1 


The  Chemistry  and  Literature 
of  Beryllium 


BY 


CHARLES  LATHROP  PARSONS,  B.  S. 


PROFESSOR  OF  INORGANIC  CHEMISTRY  IN 
NEW  HAMPSHIRE  COLLEGE 


EASTON,  PA.: 
THE  CHEMICAL  PUBLISHING  CO. 


LONDON,   ENGLAND  : 
WILLIAMS  &  NORGATE 

14    HENRIETTA  STREET,  COVENT  GARDEN,  W.  C. 


COPYRIGHT,  1909,  BY  EDWARD  HART. 


PREFACE. 


This  book  is  written  with  the  main  object  in  view  of  saving 
preliminary  study  and  labor  to  future  investigators  of  beryllium 
and  to  point  out  some  pf  the  peculiarities  of  this  interesting  ele- 
ment which  are  apt  to  lead  the  novitiate  toward  erroneous  con- 
clusions. Especially  is  it  desired  to  call  attention  to  the  fact  that 
a  large  proportion  of  its  accredited  compounds  are  in  reality  but 
indefinite  solid  solutions.  This  condition  of  the  literature  of 
beryllium  is  due  to  the  abnormal  extent  to  which  its  hydroxide 
is  soluble  in  solutions  of  its  normal  salts,  giving  rise  to  solids  of 
almost  any  degree  of  basicity  or  to  solutions  with  decreased 
osmotic  effects.  Accordingly,  results  of  analysis,  freezing  points, 
etc.,  give  little  evidence  of  the  true  nature  of  its  compounds,  un- 
less accompanied  by  proved  definiteness  of  composition,  a  proof 
too  often  omitted  throughout  the  whole  field  of  inorganic  chem- 
istry, but  nowhere  more  than  in  studying  beryllium  and  its  com- 
pounds. 

More  labor  has  been  expended  upon  the  bibliography  than  its 
limited  extent  may  seem  to  indicate.  It  is  believed  that  it  will 
be  found  to  contain  references  to  all  or  nearly  all  the  original 
articles  on  beryllium  and  that  the  references  to  abstracts  will  also 
be  found  fairly  complete  through  1902.  Since  1902  the  original 
articles  and  chief  abstracts  have  alone  been  entered.  It  has  been 
deemed  advisable  to  include  a  brief  abstract,  at  times  critical  in 
tone,  of  each  article,  but  it  is  not  claimed  that  these  abstracts  al- 
ways cover  the  full  subject  matter  of  the  original,  although  nothing 
important  is  intentionally  omitted. 

The  Journals  examined  are  approximately  the  same  as  those 
listed  in  James  Lewis  Howe's  unexcelled  Bibliography  of  the 
Platinum  Metals  and  the  plan  followed  is  in  general  the  same 
as  outlined  by  him.  The  abbreviations  used  are  familiar  to  all 
chemists. 

Grateful  acknowledgments  are  due  especially  to  the  libraries 


IV  PREFACE 

of  the  Massachusetts  Institute  of  Technology,  the  Library  of 
Harvard  University,  the  Boston  Public  Library  and  to  the  Library 
of  the  American  Academy  of  Arts  and  Sciences.  Also  to  the 
Boston  Atheneum  and  to  the  libraries  of  Columbia  University, 
N.  Y.,  and  the  Surgeon  General's  Office  and  the  Patent  Office  in 
Washington.  The  author  also  desires  to  express  his  thanks  and 
appreciation  of  a  grant  allowed  him  by  the  American  Asso- 
ciation for  the  Advancement  of  Science  toward  expenses  incurred 
in  the  preparation  of  the  Bibliography. 

CHARLES  L.  PARSONS. 
Durham,  N.  H.,  Oct.  i,  1908. 


TABLE  OF  CONTENTS. 


PART  I. 

Chapter  I.     Introduction i-io 

Discovery,  name,  history,  occurrence,  preparation  from 
beryl,  detection,  separation,  determination. 

Chapter  II.     Metallic  Beryllium 1 1-16 

Preparation,  properties,  valency,  alloys. 

Chapter  III.     Normal  Compounds  of  Beryllium    X7~44 

Discussion,  fluoride,  chloride,  bromide,  iodide,  oxide, 
sulphide,  selenide,  telluride,  trinitride,  phosphide,  cyan- 
ide, carbide,  borocarbide,  silicide,  hydroxide,  chlorate, 
bromate,  iodate,  sulphates,  sulphite,  thiosulphite,  dithion- 
ate,  sulphocyanate,  selenate,  selenite,  tellurate,  tellurite, 
chromite,chromate,  molybdate,  nitrate,  nitrite,  phosphate, 
hypophosphate,  pyrophosphate,  phosphite,  pyrophos- 
phite,  vanadate,  arsenate,  antimonate,  columbate,  carbon- 
ate, silicates,  silicotungstate,  fluosilicate,  aluminate,  fer- 
rocyanide,  ferricyanide,  nitro  prusside,  beryllium  ethyl, 
beryllium  methyl,  beryllium  propyl,  formate,  acetate, 
propionate,  acetylacetonate,  oxalates,  tartrates,  succin- 
ate,  picrate,  alpha-bromcamphor  sulphonaie,  rhodizon- 
ate,  kroconate,  citraconate,  fumarate,  maleate. 

Chapter  IV.     Acid  Salts  of  Beryllium 45*4^ 

Discussion,  mono  acid  phosphate,  acid  arsenate,  acid 
selenites,  acid  oxalate,  acid  molybdate. 

Chapter  V.     Double  Salts  of  Beryllium 47-60 

Discussion,  double  chlorides,  fluorides,  iodides,  sulphides, 
cyanides,  sulphates,  sulphites,  nitrites,  phosphates,  car- 
bonates, oxalates,  tartrates,  racemates,  malates. 

Chapter  VI.     Basic  Compounds  of  Beryllium 61-71 

Discussion,  basic  acetate,  basic  formate,  basic  propionate, 
basic  isobutyrate,  basic  butyrate,  basic  isovalerate,  in- 
definite basic  solid  phases,  basic  sulphates,  basic  oxalates, 
basic  carbonates,  miscellaneous  basic  solid  phases. 

PART  II. 

Bibliography  of  Beryllium 72-168 

Authors'  Index 

Subject  Index 


PART  I. 


CHAPTER  I. 


INTRODUCTION. 

Discovery. — In  1797  L.  N.  Vauquelin  undertook  to  prove  the 
chemical  identity  of  the  emerald  and  beryl,  which  had  already 
been  suspected  by  Haiiy,  and  in  the  course  of  his  analytical 
research,  discovered  that  a  portion  of  the  precipitate  which  had 
previously  been  supposed  to  be  aluminium  hydroxide,  was  thrown 
out  of  its  solution  in  potassium  hydroxide  on  boiling.  He  also 
found  that  this  new  hydroxide  was  soluble  in  ammonium  car- 
bonate, formed  no  alum  and  was  in  many  ways  different  from 
aluminum.  These  observations  led  him  to  announce  in  a  paper 
read  before  the  Institute  on  Feb.  14,  1898  (1798;  i),1  the  dis- 
covery of  a  new  "earth." 

Name. — In  his  first  articles  on  the  subject  (1798;  i,  2  and  3), 
Vauquelin  refers  to  the  newly  discovered  oxide  as  "la  terre  du 
Beril,"  which  was  translated  into  German  as  "Beryllerde,"  from 
which  the  name  Beryllium  took  its  rise.  At  the  end  of  Vauque- 
lin's  first  article,  the  editors  of  the  Annales  de  Chimie  suggested 
the  name  "glucine,"  for  the  new  oxide,  and  Vauquelin  in  his 
fourth  publication  (1798;  4)  adopts  the  suggestion  prefacing  its 
use  with  the  remark  "on  a  donne  le  nom  de  glucine."  As  early 
as  1799,  Link  (1799;  3)  had  objected  to  the  use  of  this  term  as 
too  closely  resembling  "glycine,"  already  in  use,  and  indeed. 
Vauquelin,  himself  (1798;  3)  seems  to  have  accepted  it  with 
reluctance.  In  1800  Klaproth  (1800;  i)  objected  to  its  use 
because  the  salts  of  the  yttrium  earths  were  also  sweet  and 
Ekeberg  (1802;  i)  agrees  with  this  idea.  The  name  "Beryl- 
lium" itself  was  used  when,  in  1828,  Wohler,  (1828;  2)  for  the 
first  time,  separated  the  metal.  For  the  sake  of  uniformity  in 
general  usage  which  is  overwhelmingly  in  favor  of  the  name 
1  References  are  to  Bibliography,  Part  II. 


2  CHEMISTRY  OF   BERYLLIUM 

derived  from  beryl,  and  as  "glucine"  grew  into  use  in  French 
literature  without  being  proposed  by  the  discoverer,  much  as 
"beryllerde"  in  Germany,  and  for  the  reasons  set  forth  in  1904, 
1 1  and  1905,  2,  it  has  been  deemed  advisable  to  adopt  the  name 
"Beryllium,"  already  in  use  by  far  the  majority  of  chemists. 

History. — Following  the  discovery  of  the  element,  Vauquelin 
studied  and  announced  the  properties  of  some  of  its  chief  com- 
pounds. In  1828  the  metal  itself  was  produced  in  a  very  impure 
form  by  both  Wohler  (1828;  2)  and  Bussy  (1828;  3).  Awdejew 
(1842;  2)  added  materially  to  the  literature  of  the  subject  and 
made  the  first  determinations  of  the  atomic  weight  that  have  any 
claim  to  accuracy.  Weeren  (1854;  i)  and  Debray  (1855;  i) 
also  carried  on  extensive  investigations  of  the  metal,  its  atomic 
weight  and  chief  compounds.  Joy  (1863;  i)  undertook  an  ex- 
tended research  on  the  preparation  of  its  compounds  from  beryl 
and  published  a  fairly  complete  bibliography  of  the  subject  to 
his  day.  Atterberg  and  Nilson  and  Pettersson  in  the  years  be- 
tween 1873  and  1885,  made  large  additions  to  the  chemistry  of 
beryllium,  and  during  these  years  a  long,  earnest  and  interesting 
discussion,  which  had  begun  as  early  as  Awde Jew's  time,  was 
carried  on  by  Nilson  and  Pettersson,  Humpidge,  Reynolds,  Hart- 
ley, Lothar  Meyer,  Brauner,  and  others  regarding  the  valency 
of  beryllium  and  its  place  in  the  periodic  system.  The  discus- 
sion has  continued  up  to  the  present  day,  but  was  in  reality 
settled  when  Nilson  and  Pettersson  (1884;  7,  8)  determined  the 
vapor  density  of  the  chloride,  and  Humpidge  (1886;  i)  showed 
that  at  high  temperatures  the  specific  heat  of  beryllium  ap- 
proached very  closely  to  normal.  Kruss  and  Moraht  (1890;  4 
and  5)  made  a  re-determination  of  the  atomic  weight  in  1890,  and 
between  the  years  1895  and  1899,  Lebeau  published  an  important 
series  of  articles  which  are  summed  up  by  him  (1899;  n)  in 
one  of  the  very  best  articles  on  beryllium  and  its  compounds. 
Urbain  and  Lacombe  (1901;  2)  and  Lacombe  (1902;  3)  dis- 
covered the  remarkable  basic  salts  of  the  acetic  acid  series  and 
Parsons  re-determined  the  atomic  weight  by  new  methods  (1904; 
5,  1905;  5)  and  studied  many  compounds,  especially  the  so-called 
basic  salts  of  some  of  the  earlier  writers  (1904;  10,  1906;  i,  2, 


INTRODUCTION  3 

3,  4,  13,  1907;  3,  10,  n).  Numerous  other  investigators  as  will 
be  seen  from  the  bibliography,  have  also  contributed  to  the 
chemistry  of  beryllium. 

Occurrence. — The  chief  form  in  which  beryllium  is  found  in 
nature  is  the  silicate,  beryl,  Be3Al2(SiO3)6,  (BeO,  13.5  per 
cent.)  including  its  gem  forms,  emerald  and  aqua  marine  and 
from  this  mineral  most  of  the  beryllium  investigators  have  de- 
rived their  material.  Beryllium  compounds  have  also  been  de- 
rived from  gadolinite,  Be,F3(YO)2(SiO4)2,  (BeO,  10  per  cent.) 
and  leucophane,  Na(BeF)Ca(SiO3)2,  (BeO,  10.3  per  cent). 
Other  important  minerals  containing  this  element  are  chryso- 
beryl,  Be(AlO2)2,  (BeO,  19.2  per  cent.);  phenacite,  Be2SiO4, 
(BeO,  45.5  per  cent.) ;  euclase,  Be(AlOH)SiO4,  (BeO,  17.3  per 
cent.)  ;bertrandite,H2Be4Si2O9,  (BeO,  42.1  per  cent.)  ;and  eudidy- 
mite,  HNaBeSi3O8,  (BeO,  10.2  per  cent).  Helvite,  danalite, 
epididymite,  crytolite,  erdmanite,  muromontite,  alvite,  foresite 
arrhmite,  siphlite,  trimerite  and  meliphanite,  are  rare  and  complex 
silicates,  while  beryllonite,  NaBePO4,  (BeO,  19.7  per  cent.)  ; 
herderite,  (CaF)BePO4,  (BeO,  15.4  per  cent.);  hambergite, 
Be2(OH)BO3,  (BeO,  53.3  per  cent),  are  interesting  merely  from 
a  mineralogical  standpoint  as  natural  occurrence  of  the  element. 
Beryllium  has  also  been  noted  in  some  natural  waters,  in  mon- 
azite  sand,  and  in  some  aluminous  schists.  It  is  quite  probable 
that  it  would  have  been  found  more  frequently  in  rock  analysis 
if  some  simple  method  of  separating  it  from  aluminum  had 
been  earlier  known. 

Preparation  from  Beryl. — Since  beryl  is  not  directly  attacked  by 
any  acid,  except,  perhaps,  by  hydrofluoric  when  ground  to  a  dust, 
it  must  first  be  fused  with  some  flux  or  be  heated  in  the  electric 
furnace  to  a  temperature  (Lebeau,  1895;  5)  which  volatilizes 
some  of  the  silica  and  leaves  a  residue  easily  attacked  by  hydro- 
fluoric acid.  For  those  having  the  facilities,  this  latter  method 
presents  many  advantages.  Among  the  fluxes  which  can  be  suc- 
cessfully used  are  sodium  and  potassium  carbonates,  calcium  flu- 
oride, potassium  fluoride,  calcium  oxide,  and  sodium  and  potas- 
sium hydroxide.  The  fluorides  possess  the  advantage  in  subse- 
quent treatment,  in  the  comparative  ease  of  removal  of  the  large 


4  CHEMISTRY   OF  BERYLUUM 

excess  of  silica,  but  for  other  reasons  have  been  seldom  used. 
Under  average  conditions  the  caustic  alkalies,  preferably  potas- 
sium hydroxide,  give  the  most  satisfactory  results. 

Beryl  is  readily  attacked  by  about  its  own  weight  of  potassium 
hydroxide  at  a  comparatively  low  heat  in  a  silver  or  nickel  cru- 
cible, although  a  salamandar  or  carborundum  crucible  can  be 
used.  Clay,  graphite  or  iron  crucibles  are  not  available  as  they 
are  immediately  attacked.  The  fused  mass  should  be  broken  up, 
just  covered  with  water,  strong  sulphuric  acid  added  until  present 
in  slight  excess  and  the  now  gelatinous  mass  heated  and  broken 
up  until  fumes  of  sulphuric  acid  are  given  off  and  the  whole  has 
the  appearance  of  a  fine  white  powder.  The  residue  is  next 
treated  with  hot  water  when  the  sulphates  of  beryllium,  alumi- 
num, iron  and  potassium  pass  into  solution  and  on  evaporation 
most  of  the  aluminum  separates  out  as  alum  and  can  be  removed. 
The  mother  liquors,  containing  all  of  the  beryllium  together  with 
impurities,  should  be  oxidized  by  boiling  with  nitric  acid  to  con- 
vert the  iron  into  the  ferric  condition,  neutralized  with  ammonia 
and  enough  sodium  bicarbonate  crystals  added  to  saturate  the  so- 
lution. The  liquid  should  now  be  warmed  and  shaken  frequent- 
ly during  a  period  of  twenty-four  hours,  when  most  of  the  beryl- 
lium will  pass  into  solution  almost  perfectly  free  from  aluminum 
and  also  from  iron  unless  other  salts  are  present,  which  is  some- 
times the  case.  By  again  dissolving  and  re-treating  the  residue 
left  after  filtration,  practically  all  the  beryllium  will  be  found  in 
the  bicarbonate  solution.  To  this  solution  ammonium  sulphide 
is  added  to  remove  any  dissolved  iron  and  the  whole  diluted 
to  five  times  its  original  volume.  By  blowing  steam  through 
this  solution  to  the  boiling  point  the  beryllium  will  be  precipitated 
usually  as  a  fine,  granular  basic  carbonate  easily  filtered  and 
washed.  The  basic  carbonate  will  be  found  to  be  quite  pure  (1906 ; 
2)  save  for  some  two  per  cent,  of  occluded  sodium  salt,  but  its 
CO2  content  and  the  ease  of  filtration  will  vary  great- 
ly with  the  conditions  of  the  hydrolysis  and  the  length 
of  the  heating  process.  The  method  employed  by  Pollok 
(1904;  i)  possesses  some  advantages  in  that  he  uses  sodium  hy- 
droxide, dissolves  in  hydrochloric  acid  and  after  filtering  off 


INTRODUCTION  5 

the  main  part  of  the  silica,  without  evaporation,  passes  hydro- 
chloric acid  gas  through  the  filtrate,  to  the  saturation  point,  where- 
by most  of  the  aluminum  is  removed  as  the  tetrahydrated  chlo- 
ride together  with  the  remainder  of  the  silica,  and  in  a  form  which 
permits  of  easy  washing.  The  beryllium  may  then  be  recovered, 
after  oxidation  of  the  iron,  by  its  solubility  in  boiling  acid  so- 
dium carbonate,  in  which  the  impurities  ordinarily  present  are 
entirely  insoluble,  or  it  may  be  obtained  in  a  less  pure  form  by  its 
solubility  in  ammonium  carbonate,  which  is  the  method  up  to 
the  present  time  almost  universally  employed. 

The  final  separation  by  ammonium  carbonate  has  the  disadvan- 
tage that  notable  quantities  of  aluminum  and  iron  also  dissolve 
and  the  use,  in  large  quantities,  of  a  somewhat  expensive  reagent. 
It  has  the  advantage  of  yielding  the  basic  carbonate  in  a  form 
which  is  easily  washed  from  all  impurities  except  ammonia. 
As  is  the  case  when  acid  sodium  carbonate  is  used,  solution 
takes  place  much  more  readily  in  the  strongly  saturated  reagent, 
and  the  subsequent  partial  hydrolysis  is  greatly  hastened  by  large- 
ly increasing  the  mass  of  the  water  present  and  is  in  both  cases 
practically  complete  on  diluting  to  a  two  per  cent,  solution  and 
heating  to  the  boiling  point.  Steam  is  much  more  preferable 
than  direct  heating  as  the  violent  and  almost  explosive  "bump- 
ing" which  is  unavoidable  in  the  latter  case  is  thereby  entirely 
prevented.  Although  not  noted  until  very  recently,  (1906;  4) 
the  basic  carbonate  produced  in  this  manner  contains  about  two 
and  one-half  per  cent,  of  ammonia  which  can  be  removed  by  long 
boiling  in  pure  water,  which  also  gradually  removes  the  carbon 
dioxide  and  leaves  the  beryllium  in  the  form  of  the  hydroxide, 
no  more  readily  washed  than  if  it  had  been  precipitated  as  such. 
In  practice  a  much  better  method  is  to  heat  the  basic  carbonate 
in  contact  with  many  times  its  weight  of  water,  to  momentary 
boiling  with  steam,  filter  and  repeat  several  times  with  fresh 
water.  This  method  is  much  more  productive  of  results  than 
washing  with  hot  water,  and  the  carbon  dioxide  is  for  the  most 
part  retained.  The  comparatively  small  amount  of  iron  that  dis- 
solves in  acid  sodium  or  ammonium  carbonate  may  be  removed 
by  adding  ammonium  sulphide,  shaking  and  filtering  off  the  fer- 


CHEMISTRY   OF   BERYLLIUM 

rous  sulphide  with  special  precaution  as  to  its  oxidation  during- 
the  filtration.  The  hydroxide  or  basic  carbonate  thus  produced 
is  the  best  form  to  use  as  a  starting  point  in  the  production  of 
other  beryllium  compounds. 

Special  purification  from  all  other  metallic  elements  can  be 
most  readily  secured  by  conversion  into  the  basic  acetate  and  re- 
crystallization  from  hot  glacial  acetic  acid  (1906;  i).  On  the 
other  hand,  the  material  prepared  by  the  sodium  bicarbonate 
method  (1906;  2)  is  pure  except  for  a  small  amount  of  sodium 
which  can  not  be  washed  out.  This  can  be  removed  by  re-solu- 
tion in  acid  and  precipitation  with  ammonia. 

Other  methods  for  the  removal  of  iron,  aluminum,  etc.,  will 
be  noted  under  analysis. 

SEPARATION  AND  DETERMINATION. 

Except  in  the  case  of  such  pure  salts  as  can  be  directly  ig- 
nited to  the  oxide,  beryllium  is  precipitated  as  the  hydroxide, 
by  ammonia  or  ammonium  sulphide,  washed  with  water  to  which 
a  little  ammonium  acetate  or  nitrate  has  been  added  (1906; 
2)  and  ignited  to  the  oxide.  When  alone,  its  determination 
presents  no  difficulty  except  the  great  tendency  of  the  hydroxide 
to  pass  through  the  filter  in  the  colloidal  state  when  washed  with 
pure  water.  This  is,  however,  entirely  overcome  by  the  use  of 
ammonium  acetate  or  nitrate  as  already  noted. 

Detection. — Follow  the  customary  procedure  of  qualitative 
analysis  until  the  sulphides  insoluble  in  HC1  have  been  removed. 
Concentrate  the  filtrate  so  obtained  to  25  cubic  centimeters  and 
when  cold  add  two  grams  solid  Na2O2,  boil  and  filter.  Acidify 
the  filtrate  with  HNO3  and  add  ammonia  in  excess.  If  no  pre- 
cipitate is  obtained  beryllium  is  absent.  Wash  any  precipi- 
tate formed  and  add  it  together  with  two  to  three  grams  solid 
NaHCO3  to  20  cubic  centimeters  (10  per  cent,  solution)  of 
water  in  a  test-tube  or  casserole  and  bring  rapidly  to  boiling. 
Boil  for  one-half  minute  only  and  filter  to  remove  all  aluminum. 
Dilute  the  filtrate  with  10  volumes  of  water  (one  per  cent,  so- 
lution) and  boil.  Beryllium  hydroxide  containing  a  little  car- 
bonate will  precipitate  if  present.  Other  elements  do  not  in- 
terfere. 


INTRODUCTION  7 

Separation. — In  minerals  and  in  admixture  with  other  ele- 
ments, the  ordinary  treatment — to  separate  aluminum  and  iron — 
should  be  followed  and  the  beryllium  will  be  found  together 
with  these  two  elements  in  their  final  separation.  It  is  quite 
probable  that  beryllium  has  been  weighed  and  calculated  as  alu- 
minum in  many  mineral  and  rock  analyses. 

Many  methods  of  separation  of  beryllium  from  iron  and  from 
aluminum,  have  been  followed,  although  most  reported  analyses 
depend  on  the  solubility  of  beryllium  hydroxide  in  ammonium 
carbonate.  Vauquelin  (1798;  i)  proposed  the  use  of  ammonium 
carbonate,  but  his  first  separation  depended  upon  the  solubility 
of  beryllium  hydroxide  in  potassium  hydroxide  and  its  precipi- 
tation on  boiling.  Gmelin  (1840;  i)  and  SchafFgotsch  (1840; 

2)  both  used  this  same  method,  but  it  is  very  far  from  being  ac- 
curate.    Scheerer    (1842;   3)    first  proposed  the   separation   of 
the  last  traces  of  iron  from  the  ammonium  carbonate  solution 
by  means  of  ammonium  sulphide.     Berthier  (1843;  2)  suggested 
the  use  of  ammonium  sulphite  as  a  reagent,  but  the  method  was 
shown  to  be  valueless  by  Bottinger  (1844;  i).     In  1850,  Rivot 
(1850;  i)  proposed  the  ignition  of  the  mixed  oxides  in  a  current 
of  hydrogen,  whereby  the  iron  was  reduced  to  metal  and  could 
be  dissolved  out  with  dilute  nitric  acid,  or  its  mass  determined  by 
the  loss  in  weight.     Debray   (1855;   i)   developed  a  separation 
dependent  upon  the  action  of  zinc  on  the  mixed  sulphates,  pre- 
cipitating the  aluminum  as  a  basic  sulphate,  but  the  method  was 
never  claimed  to  be  quantitative.     Joy  (1863;  i)  made  a  com- 
parative study  of  all  methods  proposed  to  his  time.     Gibbs  (1864; 

3)  first  suggests  the  use  of  sodium  fluoride,  to  quantitatively 
separate  aluminum  from  beryllium,  and  Pollok  (1904;  i)  shows 
that  the  fluoride  separation  is  exceedingly  sharp.     Cooke  (1866; 
i )  after  reducing  the  iron  in  hydrogen,  volatilizes  it  in  a  current 
of  hydrochloric  acid  gas.  Havens  and  Way  (1899;  5)  accomplished 
the  same  result  without  previous  reduction  of  the  oxide.     Ross- 
ler  (1878;  9)     succeeded     in     separating  beryllium  from  small 
amounts  of  aluminum  by  precipitating  with  ammonium  phosphate 
in  presence  of  citric  acid.  Vincent  (1880;  2)  uses  dimethylamine 
to  precipitate  beryllium  salts  and  finds  that  the  aluminum  com- 


8  CHEMISTRY   OF  BERYLLIUM 

pound  is  soluble  in  excess  of  the  reagent;  iron  acts  like  beryl- 
lium. Renz  (1903;  4)  confirms  this,  states  the  same  to  be  true 
of  methyl,  ethyl,  and  diethylamine  and  claims  the  results  to  be 
quantitatively  accurate.  Zimmermann  (1887;  5)  returns  to  the 
old  potassium  hydroxide  method  without  any  special  addition. 
JSchleier  (1892;  6),  Atkinson  and  Smith  (1895;  9),  and  Burgass 
(1896;  7)  separate  iron  quantitatively  from  beryllium  by  nitroso- 
beta-naphthol.  Lebeau  precipitates  the  iron  in  nitric  acid  solu- 
tion with  ferrocyanide,  the  excess  of  ferrocyanide  with  copper 
nitrate  and  the  copper  as  sulphide.  Hart  ( 1895 ;  6)  removes 
the  major  part  of  both  iron  and  aluminum  by  careful  precipita- 
tion of  the  sulphates  with  sodium  carbonate,  the  beryllium  being 
the  last  to  precipitate,  owing  to  the  great  solubility  of  its  own 
hydroxide  in  its  own  sulphate.  Havens  (1897;  4)  separates 
beryllium  from  aluminum  quantitatively  by  the  insolubility  of 
aluminum  chloride  tetrahydrate  in  a  mixture  of  hydrochloric  acid 
and  ether,  which  has  been  saturated  with  hydrochloric  acid  gas, 
and  Follok,  (1904;  i)  uses  this  same  method  for  preparation 
purposes,  omitting  the  ether.  WyroubofF  (1902;  2)  precipitates 
beryllium  as  the  double  oxalate  with  potassium  from  hydrochlo- 
ric acid  solution.  Classen  (1881;  3)  electrolyzes  in  presence  of 
oxalate  of  ammonium,  the  beryllium  being  dissolved  in  the  car- 
bonate of  ammonium  formed.  Haber  and  Van  Oordt  (1904; 
4)  dissolve  basic  beryllium  acetate  in  chloroform,  leaving  iron 
and  aluminum  acetates  behind.  Myers  (1904;  7)  removes  iron 
electrolytically  from  a  slightly  acid  solution  of  the  sulphate, 
using  a  mercury  cathode.  Parsons  and  Robinson  (1906;  i)  sep- 
arate basic  beryllium  acetate  in  a  pure  state  from  other  acetates, 
by  means  of  its  ready  solubility  in  hot  glacial  acetic  acid  and 
comparative  insolubility  in  the  same  reagent  when  cold.  Par- 
sons and  Barnes  (1906;  2)  show  the  solubility  of  beryllium  hy- 
droxide in  a  saturated  solution  of  acid  sodium  carbonate,  and 
the  insolubility  of  the  hydroxide  of  iron  and  aluminum  in  the 
same  reagent.  Glassmann  (1906;  8)  rediscovers  the  sulphite 
separation  of  Berthier  (1843;  2)»  Bottinger  (1844;  i)  and  Joy 
(1863;  i),  and  the  fact  that  the  method  is  old  is  pointed  out  by 
Friedheim  (1906;  12),  Noyes,  Bray  and  Spear  (1908;  2)  give 
accurate  methods  for  its  separation  and  detection. 


INTRODUCTION  9 

Determination. — In  the  opinion  of  the  author,  the  separation 
by  means  of  acid  sodium  carbonate  offers  the  quickest,  most 
•direct  and  best  method  for  estimating  beryllium  in  admixture 
with  other  elements.  The  method  of  Havens  (1897;  4)  is 
equally  accurate  if  care  is  taken  to  fully  saturate  with  hydro- 
chloric acid  gas. 

The  first  portion  of  the  analysis  will  be  the  regular  procedure, 
followed  to  obtain  the  hydroxides  of  iron  and  aluminum  if 
present  and  the  beryllium  will  be  found  also  as  an  hydroxide  in 
this  precipitate.  The  mixed  hydroxides  of  which  less  than 
one  gram  should  be  present,  are  dissolved  in  as  little  as  possible 
hydrochloric  acid,  oxidized  by  a  little  nitric  acid,  ammonia  added 
to  nearly  neutralize  and  evaporated  to  about  25  cubic  centimeters. 
This  solution  is  then  heated  to  boiling  and  added  with  stirring 
to  75  cubic  centimeters  of  hot  (75°)  water,  containing  12  to  15 
grams  of  the  pure  crystallized  acid  sodium  carbonate.  The 
beaker  which  contained  the  chloride  is  rinsed  with  a  little  hot 
water  and  the  whole  brought  immediately  to  boiling  and  held 
there  for  one-half  minute.  Care  must  be  taken  not  to  confuse 
the  evolution  of  carbon  dioxide  with  the  actual  boiling  of  the 
liquid,  which  must  take  place.  Under  these  conditions  the  beryl- 
lium hydroxide  passes  into  solution,  and  the  aluminum  and  ferric 
hydroxides  are  precipitated  carrying  with  them  a  small  amount 
of  beryllium.1  The  liquid  is  allowed  to  cool  and  settle  and  is 
filtered  into  a  liter  beaker  and  washed  three  times  with  a  hot 
(75")  solution  of  acid  sodium  carbonate  containing  100  grams 
to  the  liter.  The  precipitate  is  now  redissolved  in  hydrochloric 
acid  and  treated  as  before,  allowing  the  filtrates  and  washings 
to  run  into  the  same  beaker  as  first  used.  The  filtrate  is  now 
carefully  acidified  with  hydrochloric  acid,  the  beaker  being 
covered  to  prevent  loss  by  spattering,  is  boiled  to  remove  all 
carbon  dioxide  and  the  beryllium  precipitated  as  hydroxide  by 
ammonia,  avoiding  any  large  excess.  The  precipitate  is  allowed 
to  settle,  the  supernatant  liquid  decanted  through  the  filter  and 
the  precipitate  washed  twice  with  hot  water,  redissolved  in  a  lit- 

1  Uranium  may  interfere  as  has  been  pointed  out  ( 1908;  2)  but  it  is  sel- 
dom present  with  beryllium  and  may  be  easily  detected  by  ferrocyanide 
and  its  separation  presents  no  difficulty. 


10  CHEMISTRY   01?  BERYLLIUM 

tie  hydrochloric  acid  and  again  precipitated  with  ammonia 
to  remove  sodium  salts  invariably  occluded  in  the  first 
precipitation.  The  precipitate  is  now  washed  with  hot  water 
containing  two  per  cent,  ammonium  acetate  or  nitrate  until  the 
washings  give  no  chlorine  reaction.  The  hydroxide  is  ignited 
to  the  oxide  in  a  platinum  crucible  without  previous  drying,  and 
weighed. 


CHAPTER  II. 


METALLIC  BERYLLIUM. 

Preparation. — 'Beryllium  was  first  prepared  in  the  elementary 
state  by  Wohler  (1828;  2)  and  by  Bussy  (1828;  3),  acting  in- 
dependently, by  the  action  of  potassium  on  the  anhydrous  chloride. 
Davy  (1809;  i)  had  previously  attempted  to  reduce  the  oxide 
without  success  and  Stromeyer  (1812;  i)  claimed  to  have  re- 
duced the  oxide  by  a  mixture  of  carbon,  iron  and  linseed  oil  in 
1812.  Wohler  according  to  the  records  has  priority  over  Bussy 
and  deserves  further  credit  in  that  he  made  a  careful  study  of 
his  product,  which  being  very  impure  led  him  to  announce 
some  properties  since  shown  to  be  erroneous.  Debray  ( 1855 ;  i ) 
substituted  sodium  for  potassium  and  passed  his  chloride,  in 
the  sublimed  state,  over  the  melted  metal.  Menier  (1867;  i) 
exhibited  a  sample  of  metallic  beryllium  at  the  Paris  Exposition, 
which  he  had  prepared  by  the  action  of  sodium  upon  a  mixture 
of  ben-Ilium  chloride  and  the  double  fluorides  of  beryllium  and 
potassium  in  a  crucible  of  pure  aluminum.  Reynolds  (1876;  3) 
reduced  the  chloride  by  sodium,  and  Nilson  and  Pettersson 
(1878;  3  and  4)  used  the  same  method  and  succeeded  in  obtain- 
ing a  metal  of  87  per  cent,  purity  by  fusing  under  a  salt  cover 
in  a  crucible  of  iron  tightly  closed.  Again  (1880;  6  and  7)  the 
same  authors  succeeded  in  procuring  a  metal  of  94  per  cent,  purity 
but  it  was  not  until  Humpidge  (1885;  I,  1886;  i)  made  his 
final  specific  heat  determinations  in  1885,  that  a  metal  of  as 
high  a  degree  of  purity  as  99.2  per  cent,  was  obtained.  Wink- 
ler  (1890;  3)  claimed  to  have  reduced  the  oxide  by  magnesium 
and  Goldsmith  (1898;  14)  by  aluminum,  but  both  chemists  were 
undoubtedly  mistaken.  Kriiss  and  Moraht  (1890;  4  and  5)  re- 
duced the  double  fluoride  of  beryllium  and  potassium  with 
sodium,  obtaining  their  metal  in  hexagonal  plates.  Pollok  (1904; 
i  and  9)  again  produced  the  metal  by  decomposition  of  the 
chloride  with  sodium,  and  states  that  he  was  unable  to  fuse  to- 


12  CHEMISTRY   OF   BERYLLIUM 

gether  the  dark  gray  powder  formed  for  the  reason  that  it 
probably  volatilizes  at  ordinary  temperatures  without  passing 
through  the  liquid  condition. 

It  was  left  to  Lebeau  (1898;  3)  to  develop  an  apparently  sim- 
ple and  easy  method  for  producing  the  metal  almost  free  from 
admixture,  which  he  did  by  electrolyzing  the  double  fluoride  of 
beryllium  and  of  potassium  or  of  sodium  in  a  nickel  crucible.  It 
is  true  that  Warren  (1895;  10)  had  claimed  to  manufacture  the 
metal  by  the  electrolysis  of  the  bromide  which  does  not  conduct 
electricity,  and  Borchers  (1895;  n)  had  proposed  the  prepara- 
tion by  means  of  electrolyzing  the  chloride,  mixed  with  an  alkali 
chloride  but  apparently  without  result.  Lebeau  proved  that  the 
halides  of  beryllium  did  not  conduct  electricity  so  he  added 
sodium  fluoride  to  beryllium  fluoride,  melted  the  mass  in  a  nickel 
crucible  which  itself  became  the  cathode,  and  using  a  carbon 
anode,  passed  a  current  from  a  dynamo  yielding  normally  20 
amperes  at  80  volts.  Care  was  exercised  to  keep  the  heat  but 
little  above  tne  melting  point  and  metal  was  obtained  in  hex- 
agonal crystals. 

Some  patents  of  Liebermann  (1898;  15  and  16)  and  Kiihne 
(1907;  2)  for  the  production  of  beryllium  would  appear  to  be 
of  very  doubtful  value. 

Physical  Properties. — Beryllium  is  a  hard;  dark  steel  gray 
metal,  which  especially  in  its  crystal  form  has  a  bright  metallic 
luster.  The  crystals  produced  by  electrolysis  (Lebeau,  1898; 
3,  1899;  n)  are  hexagonal  lamallae,  placed  one  on  the  other 
and  according  to  Brogger  and  Flink  (1884;  4)  occur  in  two 
forms,  prismatic  and  tabular,  belonging  to  the  holohedral  division 
of  the  hexagonal  system  and  having  an  axis  relation  of  a:c=i : 
1.5802. 

The  specific  gravity  of  the  crystals  is  1.73  at  15°  (Lebeau,  1899 ; 
n),  of  the  metal  produced  by  reduction  with,  sodium  1.85  at 
20"  (Humpidge,  1886;  i).  Other  published  figures  were  on  im- 
pure material  and  need  not  be  given. 

The  melting  point  is  not, known  for  at  ordinary  pressures  and 
in  an  inert  atmosphere  it  volatilizes  without  fusion,  (Pollok; 
1904;  i).  Under  pressure  it  can  be  fused  (Nilson  and  Fetters- 


METALLIC   BERYLLIUM  13 

son,   1878;  3)   but  no  determinations  of  the  temperature  have 
been  made. 

The  specific  heat  at  ordinary  temperatures  is  abnormal  as  in 
the  case  of  boron,  carbon  and  silicon,  but  Humpidge  (1885;  I, 
1886;  i)  has  shown  that  between  400°  and  500°  it  remains 
practically  constant  at  about  0.62.  The  matter  was  one  of  long 
controversy  and  the  low  results  obtained  by  Nilson  and  Petters- 
son  (1878;  3)  and  others  was  the  chief  cause  of  the  belief  in 
the  trivalency  of  beryllium.  According  to  Humpidge  (1885; 
i  and  6,  1886;  i)  the  relation  between  specific  heat  and  tem- 
peratures can  be  expressed  by  the  empirical  formula: 
K,  =  0.3756  +  0.00106  t  —  0.00000114  /*. 

According  to  Thalen  (1869;  2)  w^°  was  first  to  study  the 
spectra  of  beryllium  it  is  characterized  by  a  line  4572.0  in  the 
blue  and  4488.5  in  the  indigo  of  about  equal  intensity.  Lockyer 
(1878;  10)  finds  beryllium  lines  in  the  sun's  spectra.  Hartley 
(1883;  5)  makes  a  careful  study  of  the  arc  spectra  of  the  chlo- 
ride and  publishes  a  chart  of  the  spectra  of  beryllium,  which 
besides  the  two  lines  in  the  visible  spectra  noted  above  by  Thalen, 
he  finds  the  lines  3320.5,  3130.2,  2649.4,  2493.2,  2477.7  °*  which 
3130.2  is  the  strongest  and  most  persistent.  Rowland  and  Tat- 
nall  (1895;  4)  in  their  exhaustive  study  of  the  arc  spectra  of 
the  elements,  found  the  most  prominent  lines  for  beryllium  be- 
tween 2100  and  4600  to  be 

2348.697  2650.414  3321.218 

2350.855  2651.042  3321.486 

2494.532  3130.556  4572.869 

2494.960  3131-200 

These  observations  were  made  with  a  grating  of  21^/2  feet 
radius  and  20,000  lines  to  the  inch  on  a  photographic  plate  19 
inches  in  length  and  are  unsurpassed  for  accuracy.  Formanek 
(1900;  3)  finds  that  the  chloride  treated  with  Alkanna  tincture 
presents  a  strong  orange  red  fluorescence  and  yields  three  ab- 
sorption bands.  Soret  (1878;  11)  finds  that  solutions  of  the 
chloride  give  no  absorption  spectra  and  only  a  feeble  bluish 
iluorescence.  Crookes  (1881;  4)  found  that  beryllium  oxide, 
in  high  vacuo,  gave  a  beautiful  blue  phosphorescence,  but 


14  CHEMISTRY   OF   BERYLLIUM 

no  spectral  rays.  Hartley  (1901 ;  i)  finds  that  the  lines  x  3130.3 
and  2478.1  are  still  visible  in  solutions  of  beryllium  salts  when 
the  concentration  has  fallen  so  low  as  o.oooooi  per  cent. 

The  atomic  ivcight  of  beryllium  is  very  close  to  9.1.  The  first 
determination  was  made  by  Berzelius  (1815;  i)  early  in  the  last 
century  and  were  little  more  than  approximations.  The  cor- 
rected results  of  other  investigators  with  the  ratio  determined 
are  as  follows: 

Mean  O  =  16 

Awdejew  ( 1842  ;  2 )                             BeO  :  BaSO4 9 .34 

Weeren  (1854  ;  i)                               BeO  :  BaSO4 9.27 

Debray  (1855  ;  i)                                 BeO  :  4CO2 9.34 

Klatzo  ( 1869  ;  i )                                   BeO  :  BaSO4 9. 28 

Nilson  and  Pettersson  (1880  ;  6)      BeSO44H,O  :  BeO  .  9.104 

Kriiss  and  Moraht  (1890  ;  5)             BeSO4-4H2O  :  BeO  .  9.05 

fBe(C6H7Oa)r-BeO.  9- "3 

Parsons  (1904  ;5)                            JBe4O(C2HsO2)6:  BeO  9.113 

f  Algebraic  combina- 

Parsons  (1905  ;  5)  •]      tion  of  above.    Be        9.112 

(.     and  C  unknown 

Chemical  Properties. — Chemically,  beryllium  is  a  metal  slight- 
ly less  basic  in  its  nature  than  magnesium.  According  to  Brau- 
ner  (1881;  i)  the  chemical  nature  of  beryllium  may  be  summed 
up  by  the  three  statements : 

Si  :  Be   =  Be  :  B, 

Si  :  Na  =  Be  :  Mg  =  B  :  Al, 

Si  :  Mg  =  Be  :  Al    =  =  B  :  Si. 

Beryllium  is  not  altered  in  dry  air  nor  in  oxygen  at  ordinary 
temperatures  but  takes  fire  when  highly  heated  and  if  finely 
divided  yields  bright  sparks  in  the  flame  of  a  Bunsen  burner. 
(Lebeau,  1899;  n).  It  combines  directly  and  easily  with  fluorine, 
chlorine  and  bromine  (Lebeau,  1898;  3)  and  with  iodine  when 
heated  in  its  vapor  (Wohler,  1828;  2)  and  (Debray,  1855;  i). 
Wohler  claimed  to  make  a  sulphide  by  heating  in  sulphur  vapor 
but  Fremy,  (1853;  i)  and  Debray,  (1855;  i)  were  unable  to 
get  the  two  elements  to  combine  directly  and  it  has  not  since 
been  produced  in  this  manner.  Strong  sulphuric  acid  attacks 
beryllium,  giving  off  sulphur  dioxide.  Hydrochloric  acid  and 
dilute  sulphuric  acid  as  well  as  solutions  of  the  caustic  alkalies 


METALLIC     BERYLLIUM  15 

attack  the  metal  with  evolution  of  hydrogen.  The  gaseous  hy- 
dracids  attack  it  violently  if  passed  over  the  heated  metal. 
Strong  nitric  acid  has  little  effect  upon  the  metal  but  weaker 
acid  attacks  it  giving  off  nitric  oxide.  It  is  but  little  acted  upon 
by  cold  water,  but  is  slowly  converted  into  the  hydroxide  by 
boiling  water. 

Beryllium  acts  upon  methyl  and  ethyl  iodides,  (Cahours,  1860; 
i)  replacing  the  iodine  and  forming  beryllium  ethyl  and  beryl- 
lium methyl.  It  also  replaces  mercury  in  its  analogous  com- 
pound and  in  mercury  propyl,  (Cahours,  1873;  I,  Lawroff,  1884; 

3). 

Wohler  ( 1828 ;  2 )  thought  he  had  prepared  the  selenide,  telluride, 
arsenide  and  phosphide  by  fusing  with  the  respective  elements 
but  his  observations  have  not  been  confirmed.  Beryllium  has 
probably  never  been  obtained  in  combination  with  hydrogen 
although  Winkler,  (1891 ;  3)  thought  he  had  produced  a  hydride. 
Beryllium  unites  directly  with  carbon,  boron  and  silicon  at  the 
heat  of  the  electric  furnace  (Lebeau,  1895;  2,  1898;  7,  1899;  I]0- 
it  reduces  SiCl4  when  heated,  (Rauter,  1892;  2). 

Valency. — 'The  valency  of  beryllium  was  long  in  doubt  and 
gave  rise  to  an  animated  discussion  extending  over  many  years 
and  calling  forth  much  research.  The  question  was  in  reality 
settled  when  Nilson  and  Pettersson,  (1884;  7)  and  (1885;  3), 
against  all  their  previous  contentions,  found  the  vapor  density 
of  beryllium  chloride  to  be  entirely  in  accord  with  the  divalency 
of  the  metal.  Their  determinations  were  made  between  490  and 
1520°  C,  and  above  1000°,  their  results  are  quite  constant  for 
the  formula  BeCl2.  The  divalency  was  confirmed  by  Humpidge 
by  the  specific  heat  at  high  temperatures  and  by  the  \iapor  den- 
sity of  both  chloride  and  bromide,  (1886;  i),  by  Coombes, 
(1894;  6)  by  the  vapor  density  of  the  acetylacetonate,  and  by 
Urbain  and  Lacombe,  (1901;  2)  by  the  vapor  density  of  the 
basic  acetate.  Rosenheim  and  Woge  (1897;  4)  also  found  the 
formula  for  the  chloride  to  be  BeCl2  by  the  rise  of  the  boiling 
point  of  its  solution  in  pyridine. 

Alloys  of  Beryllium. — Our  knowledge  of  the  alloys  of  beryl- 
lium is  confined  solely  to  the  work  of  Lebeau  (1897;  8,  1898; 


l6  CHEMISTRY   OF  BERYLLIUM 

4,  1899;  n)  and,  although  he  produced  alloys  with  the  common 
metals  and  Cr,  Mo  and  W,  he  describes  those  of  copper  only. 
His  alloys  were  made  either  by  heating  the  mixed  oxides  of 
beryllium  and  the  metal  to  be  alloyed  with  an  intimate  mixture 
of  carbon  to  a  very  high  temperature  in  the  electric  furnace,  or 
they  are  produced  simultaneously  with  the  electrolytic  produc- 
tion of  beryllium,  by  substituting  a  graphite  for  the  nickel  cru- 
cible and  fusing  in  this  the  metal  to  be  alloyed,  while  the  double 
fluoride  of  beryllium  and  sodium  was  being  electrolyzed  in  the 
same  crucible.  Alloys  of  about  10  per  cent.  Be  to  90  per  cent. 
Cu  are  pale  yellow,  nearly  white.  Alloys  of  5  per  cent.  Be  are 
yellow,  easily  polished  and  malleable,  cold  or  hot.  They  are  not 
oxidized  in  the  air,  but  are  tarnished  by  hydrogen  sulphide. 
They  are  dissolved  by  nitric  acid  with  difficulty.  As  little  as 
0.5  per  cent,  of  beryllium  changes  very  noticeably  the  appear- 
ance of  the  copper  and  makes  it  decidedly  sonorous.  An  alloy 
containing  1.32  per  cent,  of  beryllium  has  the  color  of  gold  and 
is  very  sonorous.  Tt  is  easily  polished  and  can  be  readily  forged. 


CHAPTER  III. 


NORMAL  COMPOUNDS  OF  BERYLLIUM. 

All  normal  compounds  of  beryllium  which  are  soluble  in  water 
are  strongly  acid  in  reaction  to  litmus,  dissolve  notable  quanti- 
ties of  their  own  hydroxide  which  increases  in  amount  with  the 
concentration  of  the  solution,  set  free  carbon  dioxide 
from  carbonates  and  attack  certain  metals.  In  short,  they 
act  in  many  respects  like  the  acids  themselves  would  act  from 
which  they  are  derived.  In  spite  of  these  facts  they  show  less 
hydrolysis,  and  consequent  smaller  concentration  of  hydrogen 
ions,  at  least  in  the  case  of  the  chloride,  nitrate  and  sulphate, 
(.Leys,  1899;  10  and  Brunner,  1900;  i)  when  treated  by  the 
well-known  method  of  sugar  inversion,  than  the  corresponding 
salts  of  iron  and  aluminum.  By  the  same  method  of  determina- 
tion, the  hydrogen  ions  are  thrown  back  into  the  undissociated 
condition  when  but  a  small  fraction  of  the  beryllium  hydroxide 
has  been  dissolved  which  the  normal  salt  is  capable  of  holding 
in  solution,  (Parsons,  1904;  10).  The  reasons  for  these  phe- 
nomena are  not  at  present  understood.  The  sulphate  has  been 
recently  studied  with  a  view  to  a  solution  of  this  problem, 
(1907;  10)  and  it  has  been  shown  that  the  addition  of  beryllium 
hydroxide  to  a  solution  of  the  sulphate,  raises  the  freezing  point 
and  diminishes  the  conductivity;  that  no  beryllium  enters  into 
the  formation  of  a  complex  anion  and  that  while  the  hydroxide 
can  be  partially  removed  by  dialysis  if  dialyzed  into  pure  water, 
there  is  little  evidence  of  a  colloid  being  present.  It  has  been 
suggested  that  we  may  have  here  a  new  instance  of  solution, 
wherein  the  solid,  when  once  dissolved,  acts  as  a  true  solvent 
for  its  own  oxide  or  hydroxide,  and  there  are  some  analogies 
which  point  strongly  to  this  view,  (1907;  n). 

To  this  same  cause,  whatever  it  may  be,  is  due  the  fact 
that  no  normal  carbonate  or  nitrite  is  known,  and  that  the 
chloride,  bromide,  iodide  and  nitrate  lose  their  anion  so  readily 
when  in  contact  with  water  that  they  can  only  be  prepared  with 


l8  CHEMISTRY  OF   BERYLLIUM 

special  precaution  against  hydrolysis  and  solution  of  the  hydrox- 
ide formed. 

BERYLLIUM  HALIDES. 

The  halides  of  beryllium,  with  the  exception  of  the 
chloride,  were  little  known  until  Lebeau  gave  them  most 
careful  study.  They  are,  excepting  the  fluoride,  only  pre- 
pared pure  in  the  absence  of  all  water.  By  careful  evaporation 
of  the  fluoride  in  the  presence  of  ammonium  fluoride  or  in  an 
atmosphere  of  hydrofluoric  acid  gas,  it  can  apparently  be  kept 
from  hydrolytic  action,  (Lebeau,  1899;  n)  but  this  is  not  true 
of  any  of  the  other  halides.  On  evaporating  their  solutions  in 
water  they  lose  more  or  less  of  the  gaseous  hydracids,  the 
residue  becoming  more  and  more  basic  and  remaining  soluble 
until  a  surprising  degree  of  basicity  is  reached.  This  hydrolytic 
action  is  comparatively  small  in  the  case  of  the  fluoride,  but  is 
practically  complete  in  the  case  of  the  chloride,  bromide  and  io- 
dide. By  careful  manipulation  residues  of  almost  any  degree  of 
basicity  can  be  obtained  and  these  mixtures  of  base  and  normal 
salt  have  given  rise  to  claims  for  numerous  oxyfluorides  and 
cxyMorides  for  the  existence  of  which  there  is  no  other  evi- 
dence than  the  analysis  of  the  variable  residues  obtained. 

Beryllium  Fluoride,  BeF2.  —  The  first  experiments  on  the 
relation  of  fluorine  to  beryllium  were  made  by  Gay 
Lussac  and  Thenard  in  1811  (1811;  i).  Later  in 
1823,  Berzelius  (1823;  i)  made  the  fluoride  by  dis- 
solving the  oxide  in  hydrofluoric  acid  and  described  the  proper- 
ties of  the  solution  so  produced  and  the  residue  left  on  evapora- 
tion, the  basic  nature  of  which  he  recognized.  Klatzo  (1869; 
i)  made  a  short  study  of  the  fluoride,  but  the  pure  salt  was  not 
produced  until  Lebeau  (1898;  8,  1899;  IT)  made  it  by  heating 
the  double  fluoride  of  ammonium  and  beryllium,  which  had  pre- 
viously been  dried  over  phosphoric  anhydride,  in  a  current  of 
dry  carbon  dioxide  and  cooled  in  an  atmosphere  of  the  same  gas. 
He  also  prepared  it  by  the  action  of  hydrofluoric  acid  gas  on 
the  carbide. 

Properties. — According  to  Lebeau  the  pure  fluoride  is  a  glassy, 
transparent  mass  having  a  specific  gravity  of  2.01  at  15°.  It 


NORMAL   COMPOUNDS  OF  BERYLLIUM  19 

becomes  fluid  towards  800°,  passing  through  a  viscous  condition, 
but  above  800°  it  begins  to  volatilize,  yielding  white  and  very 
deliquescent  crystals.  It  dissolves  in  all  proportions  in  water, 
is  only  slightly  soluble  in  absolute  alcohol,  but  dissolves  read- 
ily in  90  per  cent,  alcohol.  By  cooling  an  alcoholic  solution  to 
— 23°,  one  obtains  a  white  crystalline  mass  which,  however,  melts 
easily  on  rise  of  temperature.  It  is  also  soluble  in  a  mixture  of 
ether  and  alcohol.  The  majority  of  metalloids  are  without  action 
on  the  fluoride.  It  is  insoluble  in  anhydrous  hydrofluoric  acid 
and  is  not  altered  by  it,  rendering  the  existence  of  an  acid  salt 
quite  improbable.  It  is  readily  attacked  by  sulphuric  acid.  The 
alkali  metals  and  magnesium  reduce  it,  but  the  difficulty  of  fu- 
sion and  hydroscopicity  renders  the  preparation  of  pure  metal  dif- 
ficult. With  potassium  the  reaction  begins  below  500°.  Lith- 
ium and  magnesium  act  at  about  650°.  Aluminum  fuses  with- 
out alteration. 

Beryllium  Chloride,  BeCl2. — Although  Vauquelin  (1798;  5) 
obtained  the  chloride  in  solution,  the  pure  salt  was 
not  made  until  Rose  (1827;  i)  prepared  it  in  the 
sublimed  anhydrous  state  by  passing  chlorine  gas  over 
a  heated  mixture  of  carbon  and  beryllium  oxide.  Wohler  (1828; 
2),  Awdejew  (1842;  2),  Debray  (1855;  i),  Klatzo  (1869;  i), 
Nilson  and  Pettersson  (1880;  6,  7,  and  8,  1885;  3),  Pollok  (1904; 
12)  and  others  used  the  same  method  of  preparation.  Nilson 
and  Pettersson  (1885;  3)  prepared  the  chloride  in  very  pure 
form  for  the  purpose  of  determining  its  vapor  density  by  the 
action  of  dry  hydrochloric  acid  gas  on  the  metal.  Lebeau 
(1895;  2,  1899;  u)  utilized  the  carbide  which  is  readily  attacked 
when  heated  by  both  chlorine  and  gaseous  hydrochloric  acid. 
Lothar  Meyer  (1887;  i)  obtained  the  chloride  by  passing  car- 
bon tetrachloride  vapor  over  heated  beryllium  oxide.  Bourion 
(1907;  7)  prepares  the  chloride  by  the  action  of  a  stream  of 
mixed  Cl  .Mid  S2C1.>  on  the  oxide  at  a  red  heat.  No  matter 
what  method  is  used  the  materials  must  be  absolutely  dry  if  a 
pure  chloride  is  to  be  obtained.  Awdejew  (1842;  2)  and  Atter- 
berg  (1873;  7)  thought  they  had  produced  a  hydrous  chloride, 
BeCl24H2O,  by  evaporating  the  chloride  slowly  over  sulphuric 
acid,  but  Parsons  (1904;  5)  shows  that  the  procedure  recom- 


2O  CHEMISTRY    OF    BERYLLIUM 

mended  invariably  yields  basic  mixtures  of  varying  degrees  of 
hydration.  Atterberg's  results  are  easily  explained  when  one 
considers  that  his  formula  depended  solely  on  an  analysis  for 
chlorine  alone,  and  although  Awdejew  gives  no  details  of  his 
analytical  results,  it  is  probable  he  was  led  to  his  undoubtedly 
erroneous  conclusion  in  the  same  way. 

Properties. — The  anhydrous  chloride  is  a  white  crystalline 
solid  having  a  melting  point  about  440°  (Lebeau,  1899;  n, 
Pollok,  1904;  12).  Carnalley  (1879;  I,  1880;  I,  1884;  9,  1884; 
10)  obtained  much  higher  figures,  but  was  certainly  in  error. 
The  boiling  point  is  about  520°  as  shown  by  Nilson  and  Petters- 
son  and  confirmed  by  Pollok  (1904;  i).  Its  vapor  density  first 
determined  by  Xilson  and  Pettersson  (1884;  7,  1885;  3)  between 
490°  and  1520°,  is  in  entire  accord  with  the  formula  BeCl2.  This 
was  confirmed  by  Humpidge  (1886;  i).  Rosenheim  and  Woge 
(1897;  4)  showed  that  the  molecular  weight  as  determined  by 
the  raising  of  the  boiling  point  of  a  solution  of  beryllium  chlo- 
ride in  pyridine,  was  in  agreement  with  the  same  formula. 
Its  molecular  heat  of  solution  is  44.5K0  and  its  molecular  heat 
of  formation  is  I55K°  (Pollok,  1904;  9).  Its  magnetic  suscept- 
ibility was  determined  by  Meyer  (1899;  3).  The  fused  chloride 
does  not  conduct  the  electric  current,  (Lebeau)  but  its  alcoholic 
solution  is  a  conductor  (Pollok,  1904;  i). 

Beryllium  chloride  dissolves  in  water  with  great  avidity  and, 
unless  special  precautions  are  taken,  with  loss  of  chlorine  as 
hydrochloric  acid.  On  evaporation  the  solution  loses  hydrochlo- 
ric acid  more  or  less  readily  according  to  conditions,  and  the 
residue  left,  which  may  be  of  almost  any  degree  of  basicity,  has 
been  mistaken  for  an  oxychloride  by  Atterberg  (1873;  7,  1875; 
4).  With  ether  it  forms  the  compound  BeCl,.2[  (C2H,)2O], 
(Atterberg,  1875;  4).  It  also  forms  a  white  crystalline  com- 
pound containing  the  chloride  with  both  hydrochloric  acid  and 
ether  (Parsons,  1904;  5),  the  exact  composition  of  which  has 
not  been  determined.*  It  is  also  readily  soluble  in  alcohol,  and 
yields  a  crystalline  compound  with  it,  but  is  almost  insoluble  in 
benzene,  chloroform,  carbon  tetrachloride  and  sulphur  dichlo- 

*  Since  this  went  to  press  a  letter  from  H.  Steimnetz  informs  me  that  tfiese  crystals 
are  in  reality  BeCl8.4H7O.  It  is  accordingly  certain  from  the  conditions  that  this  com- 
pound was  never  made  by  Atterberg.  Its  indentifiration  belongs  to  Steinmetz  My  in- 
correct observation  was  qualitative  only  and  made  in  the  course  of  another  investigation. 

THE  AUTHOR. 


NORMAL    COMPOUNDS    OF    BERYLLIUM  21 

ride  (Lebeau,  1899;  n).  It  combines  with  ammonia  gas  and 
with  phosphine.  Lebeau  (1899;  n)  claims  that  it  forms  many 
crystalline  compounds  with  the  organic  bases,  but  Renz  (1903; 
3)  was  only  able  to  obtain  the  compound,  BeCl2.(C9H7N2)2-f- 
-H2O,  with  quinoline.  By  experiments  on  the  chloride  and  sul- 
phate, Hober  and  Kieson  (1898;  9)  were  able  to  show  that  their 
taste  was  due  to  the  cation.  The  chloride  forms  many  double 
salts  (vidi,  Double  Salts).  According  to  Brunner  (1900;  i) 
and  Leys  (1899;  10),  beryllium  chloride  solutions  are  less  hydro- 
hzed  than  those  of  aluminum  and  iron,  although  about  two  per 
cent,  of  the  molecules  are  so  decomposed.  Awdejew  (1842;  2) 
and  Nilson  and  Pettersson  (1884;  7,  1885;  3)  claim  that  the  sub- 
limed chloride  attacks  glass,  but  Parsons  (1904;  5)  states  that 
this  is  probably  incorrect. 

Beryllium  Bromide. — The  bromide  was  first  prepared  by 
Wohler  (1828;  2)  by  the  action  of  bromine  vapor  on  the  metal 
and  also  upon  a  mixture  of  carbon  and  beryllium  oxide.  Ber- 
themot  (1831 ;  i)  obtained  it  in  solution  by  dissolving  the  oxide 
in  hydrobromic  acid.  Humpidge  (1883;  7)  also  prepared  it  by 
acting  on  a  mixture  of  the  oxide  and  carbon  with  dry  bromine. 
Lebeau  (1899;  n)  prepared  it  by  the  action  of  bromine  and 
gaseous  hydrobromic  acid  on  the  carbide. 

Properties. — The  anhydrous  bromide  is  obtained  always  by 
sublimation  and  in  colorless  white  crystals.  Its  vapor  density 
determined  by  Humpidge  (1886;  i)  is  in  accord  with  the  for- 
mula BeBr2.  Its  melting  point  was  determined  by  Carnalley 
and  Williams  (1879;  i,  1880;  i,  1884;  9  and  10)  but  the  values 
obtained  were  much  too  high,  as  shown  by  Lebeau  (1899;  11), 
who  states  that  it  fuses  at  about  490°  and  begins  to  sublime  some- 
what below  this  temperature.  The  fused  salt  does  not  conduct 
electricity,  although  Warren  (1895;  10)  claimed  to  make  the 
metal  in  some  quantity  by  electrolyzing  it.  For  a  knowledge 
of  its  chemical  properties  we  are  indebted  almost  wholly  to 
Lebeau  (1899;  u)  who  states  that  it  acts  much  the  same  as 
the  chloride.  It  dissolves  in  water  with  avidity,  losing  hydro- 
bromic acid  on  evaporation.  It  is  soluble  in  absolute  alcohol 


22  CHEMISTRY   OF   BERYLLIUM 

and  forms  a  crystalline  compound  therewith.  It  combines  with 
ammonia  and  with  the  organic  bases. 

Beryllium  Iodide,  BeI2.— Wohler  (1828;  2)  and  Debray  (1855; 
] )  prepared  the  iodide  by  the  action  of  iodine  upon  the  metal, 
but  we  are  indebted  almost  solely  to  Lebeau  (1898;  6,  1899;  n), 
who  prepared  it  in  some  quantity  by  the  action  of  gaseous  hydri- 
odic  acid,  or  a  mixture  of  hydrogen  and  iodine  vapor,  on  the 
carbide  at  about  700°,  for  a  knowledge  of  its  properties. 

Properties. — According  to  Lebeau  (1899;  JI)>  beryllium  io- 
dide, as  obtained  in  the  sublimed  state,  consists  of  colorless 
crystals,  which  are  quickly  decomposed  in  moist  air.  Their  spe- 
cific.gravity  at  15°  is  close  to  4.20.  They  begin  to  sublime  below 
their  melting  point  which  is  510°.  The  melted  iodide  boils  be- 
tween 585°  and  595°.  It  is  insoluble  in  benzene,  toluene,  spirits 
of  turpentine,  and  but  slightly  soluble  in  carbon  disulphide. 
The  slightest  trace  of  water  attacks  it  immediately,  but  it  is  not 
quite  so  sensitive  after  fusion,  probably  because  less  sur- 
face is  exposed.  It  can  be  distilled  without  alteration  in  dry  hy- 
drogen, nitrogen  or  carbon  dioxide.  Its  iodine  is  readily  re- 
placed by  chlorine  or  bromine.  Fluorine  forms  fluorides  of  both 
beryllium  and  of  iodine.  Fluorine  and  chlorine  both  attack  it 
even  when  cold,  giving  off  heat  and  light.  Cyanogen  acts  upon 
it  at  about  a  red  heat,  producing  a  white  material,  less  volatile 
than  the  iodide,  which  with  water  gives  a  clear  solution  reacting 
for  cyanides.  Heated  in  oxygen,  it  takes  fire  at  about  a  red  heat 
and  the  vapor  itself  will  burn  even  in  air.  Heated  with  sulphur 
it  yields  a  sulphide  of  beryllium,  readily  decomposed  by  water. 
The  vapor  of  phosphorus  also  attacks  it,  probably  forming  a 
phosphide  of  beryllium.  Sodium,  potassium  and  lithium  re- 
duce it  at  about  350°.  Magnesium  reduces  it  at  about  450°. 
Aluminum,  silver,  copper  and  mercury  are  without  ac- 
tion below  the  temperature  of  the  softening  of  glass. 
Hydrogen  sulphide  acts  upon  it,  but  only  at  elevated 
temperatures  and  yields  a  white  sulphide.  It  absorbs  large 
amounts  of  ammonia  gas  and  forms  compounds  which  melt 
easily  and  can  be  crystallized  on  cooling.  It  reacts  with  a  large 
number  of  organic  compounds.  It  is  soluble  in  alcohol  and  pro- 


NORMAL    COMPOUNDS    OF    BERYLLIUM  2J 

duces  a  crystalline  compound  therewith.  It  also  combines  with 
ether.  It  differs  from  the  iodide  of  aluminum  in  not  reacting 
with  cold  tetrachloride  of  carbon.  It  also  does  not  act  upon  C2C14, 
Acetic  anhydride  and  anhydrous  chloral  give  energetic  reactions 
with  beryllium  iodide.  Ammonium  compounds  and  organic 
bases,  especially  aniline  and  pyridine,  produce  crystalline  com- 
pounds with  it. 

BERYLLIUM  OXIDE. 

Preparation. — The  oxide  is  prepared  by  heating  the  nitrate, 
sulphate,  oxalate,  hydroxide,  basic  carbonate  or  other  salt  of 
beryllium  containing  a  volatile  acid  radical,  and  even  the  chlo- 
ride, bromide  and  iodide  yield  practically  all  of  their  metal  as 
oxide  when  evaporated  from  solution  and  heated.  By  evaporat- 
ing to  dryness  a  mixed  solution  of  beryllium  chloride  and  ammo- 
nium chloride  and  heating  in  air,  an  oxide  so  light  and  feathery 
is  produced  that  it  is  difficult  to  retain  it  in  the  containing  ves- 
sel. 

Properties. — The  oxide  is  a  white  powder  as  ordinarily  pro- 
duced which  can  be  volatilized  and  crystallized  at  high  tempera- 
ture. According  to  Levi-Malvano  (1905;  7)  a  blue  oxide  is 
obtained  by  igniting  the  hexahydrated  sulphate  (vidi  sulphates).1 
In  the  electric  furnace,  (Lebeau,  1896;  6,  1899;  u)  it  can  be 
fused  and  even  volatilized  and  yields  a  crystalline  mass  slightly 
harder  than  corundum.  The  crystals  are  hexagonal  (Lebeau, 
1899;  n).  Mallard,  (1887;  4)  states  that  they  are  positive  and 
unaxial  and  he  measured  parameters  a  :h=  1 : 1.6305.  He  fur- 
ther states  they  are  isomorphous  with  zinc  oxide,  and  Ebelmen 
(1851;  i)  states  that  they  are  isomorphous  with  aluminum  ox- 
ide. The  oxide  is  diamagnetic  (Nilson  and  Pettersson,  1880; 
9)  and  its  magnetic  susceptibility  has  been  determined  by  Meyer 

(1899;  3). 

The  specific  gravity  was  first  determined  by  Ekeberg  (1802; 
i)  as  2.967.  Rose  (1848;  2)  found  3.021  to  3.09,  claiming  the 
lower  figure  was  obtained  by  high  heating.  Ebelmen  (1851;  i) 
reported  3.058;  Nilson  and  Pettersson  (1880;  9,  1880;  10)  ob- 

1  Repeated  attempts  by  the  author  of  this  book  to  reproduce  this  oxide 
or  even  the  hexahydrated  sulphate  have  met  with  failure. 


24  CHEMISTRY  OF   BERYLUUM 

tained  3.016  and  Grandeau  (1886;  2)  3.18.  Later  results  on 
very  pure  material  gave  Kriiss  and  Moraht  (1890;  7)  2.9644; 
Lebeau  (1896;  6,  1899;  n)  at  o°,  3.01-3.025;  Parsons  (1904;  5) 
at  4°,  2.9640.  According  to  Lebeau,  fusing  the  oxide  had  very 
little  effect  on  the  specific  gravity. 

The  specific  heat  of  beryllium  oxide  is  0.247  between  o°  and 
100°  (Nilson  and  Pettersson,  1880;  9  and  10).  According  to 
Tanatar  it  is  0.2898  between  100-117°. 

Crystals  of  the  oxide  have  been  produced  by  melting  in  the 
electric  furnace  (Lebeau,  1896;  6),  by  fusing  a  mixture  of  beryl- 
lium silicate  and  potassium  carbonate  (Ebelmen,  1851;  i),  by 
fusing  a  mixture  of  sulphate  of  potassium  and  sulphate  of  beryl- 
lium (Debray,  1855;  i),  by  fusing  a  mixture  of  sulphate  of  po- 
tassium and  phosphate  of  beryllium  (Grandeau,  1886;  2),  by 
dissolving  the  oxide  in  fused  beryllium  leucite  (Hautefeuille 
and  Perrey,  1890;  9)  and  by  fusing  the  sulphate  with  silicic 
acid  (Hautefeuille  and  Perrey,  1890;  14). 

Beryllium  oxide  is  not  reduced  by  hydrogen,  magnesium,  so- 
dium, potassium  or  aluminum  (Lebeau,  1896;  6,  1899;  n).  Ac- 
cording to  Franck  (1898;  20),  aluminum  does  form  alloys  at 
high  temperature  by  heating  with  beryllium  oxide.  It  is  re- 
duced by  carbon  at  high  temperatures  in  the  presence  of  other 
metals,  such  as  copper,  forming  alloys  therewith,  or,  when  treat- 
ed alone  at  high  temperatures  with  either  carbon,  boron  or  silicon 
it  is  reduced,  forming  the  carbide,  borocarbide  or  silicide  (Le- 
beau, 1899;  n).  It  is  not  acted  upon  by  water  or  carbon  di- 
oxide. Ballard  (1834;  i)  states  that  bromine  water,  especially 
under  the  influence  of  sunlight  partly  dissolves  beryllium  oxide, 
but  Lebeau  (1899;  it)  finds  that  it  is  not  affected  by  bromine, 
chlorine,  iodine  or  others  of  the  non-metals  except  fluorine,  which 
attacks  it  directly  with  the  formation  of  a  fluoride.  Mixed  with 
carbon  and  heated  in  a  current  of  a  halogen  gaS  the  correspond- 
ing halide  is  formed  and  Meyer  (1887;  i)  found  that  the  anhy- 
drous chloride  was  formed  if  the  oxide  was  heated  in  a  current 
of  carbon  tetrachloride  vapor.  Bourion  (1907;  7)  found  that  it 
was  also  acted  upon  by  S2C12  at  a  red  heat  with  the  formation 
of  the  chloride. 


NORMAL    COMPOUNDS    OF    BERYLLIUM  25 

The  gaseous  hydracids  have  no  action  on  the  oxide,  even 
at  high  temperatures.  Strong  hydrochloric  and  nitric  acids  dis- 
solve the  oxide  slowly.  Strong  sulphuric  acid  attacks  it  readily 
forming  the  anhydrous  sulphate  which  dissolves  only  slowly  on 
dilution  with  water  as  hydration  progresses.  Rose  (1848;  3, 
1855;  2)  states  that  beryllium  oxide  partially  decomposes  solu- 
tions of  NH4C1,  but  loses  this  property  if  heated.  Atterberg 
(1873;  7)  states  that  the  oxide  is  not  soluble  in  fused  potassium 
hydroxide.  According  to  Ebelmen  (1851 ;  i),  it  is  readily  solu- 
ble in  potassium  bisulphate. 

Beryllium  Sulphide. — Wohler  (1828;  2)  supposed  he  had  made 
a  sulphide  by  heating  the  metal  with  sulphur,  but  Fremy  (1853; 
i)  states  that  it  was  the  only  sulphide  he  could  not  produce  by 
passing  the  vapor  of  carbon  disulphide  over  the  hot  oxide.  De- 
bray  (1855;  0  and  Nilson  and  Pettersson  (1873;  3)  state  that 
beryllium  and  sulphur  do  not  combine  when  heated  together. 
Berzelius  (1826;  2)  supposed  he  produced  a  double  sulphide  of 
beryllium  and  tungsten,  but  his  results  lack  confirmation.  Lebeau 
(1899;  n)  at  last  made  the  sulphide  by  heating  the  anhydrous 
chloride  and  iodide  with  sulphur  or  with  hydrogen  sulphide. 
Also  by  the  action  of  sulphur  vapor  on  the  carbide  at  a  high 
temperature.  The  sulphide  is  a  white  solid,  immediately  decom- 
posed by  water.  No  other  details  are  given  nor  further  study 
of  this  compound  been  made. 

Beryllium  Selenide,  Beryllium  Telluride. — Preparation  claimed 
by  Wohler  (1828;  2),  but  probably  he  was  mistaken. 

Beryllium  Trinitride. — Attempts  to  make  the  trinitride  (Curtius 
and  Rissom,  1898;  12)  by  the  action  of  a  solution  of  beryllium 
sulphate  on  barium  trinitride  failed,  as  it  immediately  broke 
down  to  beryllium  hydroxide  and  hydronitric  acid. 

Beryllium  Phosphide.— Claimed  by  Wohler  (1828;  2),  by  the 
action  of  phosphorus  on  the  metal,  but  unconfirmed  by  this 
method.  Lebeau,  however,  (1899;  n)  prepared  a  compound  of 
beryllium  and  phosphorus,  which  he  did  not  analyze  or  describe, 
by  means  of  the  action  of  phosphorus  vapor  on  anhydrous  beryl- 
lium chloride  and  iodide. 


26  CHEMISTRY   OF   BERYLUUM 

Beryllium  Cyanide. — By  the  action  of  cyanogen  gas  on  beryl- 
lium iodide,  Lebeau  (1898;  6,  1899;  n)  produced  a  cyanide 
compound  of  beryllium  which  he  neither  studied  nor  analyzed. 

Beryllium  Carbide,  Be2C. — The  carbide  of  beryllium  has  been 
produced  by  Lebeau  (1895;  2,  1899;  n)  by  heating  a  mixture  of 
one  part  carbon  and  two  parts  beryllium  oxide  in  an  electric 
furnace,  using  a  current  of  950  amperes  and  50  volts  for  about 
ten  minutes.  Lebeau  first  gave  it  the  formula  Be4C3,  but  after 
Henry  (1895;  8)  called  his  attention  to  his  error,  he  adopted 
the  formula  Be2C.  Its  properties  are  quite  similar  to  those  of 
aluminum  carbide.  At  15°  its  specific  gravity  is  1.9.  It  is  so 
hard  it  scratches  quartz  easily.  It  consists  of  yellowish  brown 
transparent  crystals.  Fluorine,  chlorine  and  bromine  attack  it 
readily  if  heated,  forming  the  corresponding  halide  and  leaving 
a  residue  of  carbon.  Iodine  is  without  action  at  800°.  Oxygen 
attacks  it  only  superficially  when  heated.  The  vapor  of  sulphur 
reacts  at  about  1000°,  forming  the  sulphide.  Hydrofluoric  acid 
gas  attacks  it  at  about  450°,  forming  the  fluoride.  Hydrochloric 
acid  gas  forms  the  chloride  at  about  600°  and  sets  free  carbon 
and  hydrogen.  Hydriodic  acid  gas  attacks  it  at  about  750°, 
yielding  the  iodide.  Beryllium  carbide  slowly  decomposes  water 
yielding  beryllium  hydroxide  and  pure  methane.  The  reaction 
is  much  more  rapid  in  solution  of  potassium  hydroxide.  The 
carbide  reduces  concentrated  sulphuric  acid,  although  it  is  but 
slowly  attacked  by  concentrated  nitric  and  hydrochloric  acids. 
These  same  acids  diluted  dissolve  it  completely  after  a  few  hours. 
Fused  potash  attacks  it  with  incandescence  and  it  is  oxidized  by 
potassium  permanganate  and  peroxide  of  lead.  The  chlorate  and 
nitrate  of  potassium  do  not  attack  it. 

Beryllium  Borocarbide,  3Be2C.B6C. — By  heating  a  mixture  of 
boron  and  beryllium  oxide  in  a  carbon  tube  by  means  of  a  cur- 
rent of  150  amperes  and  45  volts,  Lebeau  (1898;  7,  1899;  n) 
produced  some  bright  metallic  crystals  to  which  he  gave  the  for- 
mula Be6B6C4.  The  borocarbide  has  a  specific  gravity  of  2.4  at 
15°.  It  is  not  altered  in  air  unless  heated  and  then  oxidizes  only 
superficially.  Fluorine,  chlorine,  bromine  and  iodine,  as  well  as 
their  hydracids,  act  much  the  same  as  on  the  pure  carbide.  Sulphur 


NORMAL    COMPOUNDS    OF    BfcRYLUUM  27 

attacks  it  only  superficially  at  a  red  heat.  Mineral  acids  and  es- 
pecially nitric  acid  dissolve  it  rapidly. 

Beryllium  Silicide. — Lebeau  (1899;  n)  also  obtained  a  silicide 
of  beryllium,  but  was  unable  to  purify  it  sufficiently  to  deter- 
mine its  properties  or  formula. 

Beryllium  Hydroxide,  Be(OH)2. — Beryllium  hydroxide  is  a 
white  gelatinous  mass  physically  indistinguishable  from  alu- 
minum hydroxide  and  resembling  it  very  closely  from  a  chem- 
ical standpoint.  It  is  precipitated  from  solutions  of  beryllium 
salts  by  ammonia,  ammonium  sulphide,  caustic  alkalies  and  ba- 
rium carbonate.  It  is  also  precipitated  by  methyl,  dimethyl, 
ethyl,  and  diethyl  amines  (Vincent,  1880;  2,  Renz,  1903;  4). 
Soluble  normal  carbonates  throw  down  a  basic  mass  which  con- 
sists largely  of  the  hydroxide  together  with  some  carbonate. 
The  latter  may,  however,  be  almost  entirely  eliminated  by  boil- 
ing. It  is  readily  attacked  by  solutions  of  acids.  It  dissolves 
slowly  in  concentrated  solutions  of  ammonium  carbonate  (Vau- 
quelin,  1798;  i,  et  al.)  and  sodium  bicarbonate.  It  is  imme- 
diately soluble  in  a  saturated  boiling  solution  of  sodium  bicar- 
bonate (Parsons  and  Barnes,  1906;  2).  It  is,  however,  almost 
insoluble  in  a  dilute  solution  and  a  strong  solution  which  has 
dissolved  the  hydroxide,  on  dilution  (two  per  cent,  or  less 
NaHCO3)  slowly  hydrolyzes  in  the  cold  and  throws  out  the! 
basic  carbonate  or  does  so  immediately  on  boiling.  It  is  almost 
insoluble  in  normal  sodium  carbonate.  It  is  soluble  in  sodium 
and  potassium  hydroxides  forming  beryllonates  which  are  hy- 
drolytically  decomposed  on  boiling.  This  decomposition  is  com- 
plete if  excess  of  base  is  not  present,  but  may  be  partially  or 
entirely  prevented  by  increasing  the  mass  of  the  soluble  hydrox- 
ide. It  is  soluble  in  solutions  of  its  own  salts  and  in  proportion 
to  the  concentration  of  the  particular  salt  used.  From  concen- 
trated solution  in  its  own  salts,  it  is  precipitated  by  dilution, 
but  such  precipitation  is  never  complete.  It  is  insoluble  in  ex- 
cess of  ammonium  sulphide,  ammonia,  and  methyl,  ethyl,  di- 
methyl and  diethyl  amines  (Vincent,  1880;  2,  Renz,  1903;  4). 
When  washed  with  pure  water  it  slowly  passes  through  the 
filter  in  colloidal  solution  (Parsons  and  Barnes,  1906;  2).  Beryl- 


28  CHEMISTRY   OF  BERYLLIUM 

Hum  hydroxide,  like  aluminum  hydroxide,  is  more  susceptible 
to  reaction  when  freshly  precipitated  (Haber  and  Van  Oordt, 
1904;  2).  This  is  more  especially  apparent  in  the  case  of  car- 
bon dioxide,  for  when  freshly  precipitated  it  will  absorb  about 
one  third  of  an  equivalent  of  this  gas,  but  if  allowed  to  stand 
sometime  and  especially  if  first  heated,  it  almost  entirely  loses 
this  property  (Parsons  and  Roberts,  1906;  4).  Leys  (1899;  IO) 
states  that  it  is  n  times  as  basic  as  aluminum  hydroxide.  It 
has,  like  most  other  gelatinous  hydroxides,  a  very  great  tendency 
to  occlude  other  substances  which  may  be  present  when  it  is  pre- 
cipitated and  it  is  almost  impossible  to  remove  these  substances 
by  washing.  It  is  nearly  insoluble  in  water  charged  with  car- 
bon dioxide  (Sestini,  1891 ;  6)  and  according  to  Toczynski  (1871 ; 
2)  in  hydrocyanic  acid. 

Van  Bemmelen  (1882;  2)  distinguishes  two  forms  of  the  hy- 
droxide, first  alpha,  precipitated  from  potassium  beryllonates  by 
boiling  which  form  is  easily  washed  and,  he  claims,  is  the  only 
one  of  definite  composition  being  readily  dried  to  the  formula 
Be  (OH)  2,  and  second  beta,  which  is  the  gelatinous  mass  pre- 
cipitated by  alkalies  which  is  always  more  or  less  hydrated.  At- 
terberg  (1873;  7)  gives  formulas  for  some  of  these  hydrated 
oxides,  but  there  is  little  in  his  work  or  that  of  Van  Bemmelen 
(1882;  2)  to  show  that  this  extra  water  is  other  than  mechani- 
cally held.  Reubenbauer  (1902;  5)  found  that  sodium  hydrox- 
ide dissolves  beryllium  hydroxide  in  proportion  to  its  concentra- 
tion. Van  Bemmelen  (1898;  19)  studied  the  effects  of  heat 
on  his  two  forms  of  the  hydroxide.  Meyer  (1899;  3)  deter- 
mined the  magnetic  susceptibility  of  the  hydroxide.  It  is  read- 
ily, although  slowly,  decomposed  by  boiling  with  solutions  of 
ammonium  salts  (Rose,  1848;  3),  Debray  (1855;  i),  Joy  (1863; 
i),  Parsons  (1904;  5,  et  al.).  v.  Kobell  (1832;  i)  states  that 
calcium  carbonate  will  not  precipitate  beryllium  hydroxide  in 
the  cold,  but  does  so  on  boiling.  Prudhummer  (1895  ;  7)  states 
that  beryllium  hydroxide  does  not  act  as  a  mordant. 

The  heat  of  neutralization  of  beryllium  hydroxide  as  found 
by  Thomsen  (1871;  I,  1874;  2)  is 


NORMAL  COMPOUNDS  OF  BERYLUUM  29 

Be(OH)2+H2SO4+Aq=i6ioo  calories. 
Be(OH)2+2HCl-f Aq=i3640  calories. 
Pettersson  (1890;  8)  found 

Be(OH)2-f2HF+Aq=i9683  calories. 

Gmelin  (1840;  i),  Schaffgotsch  (1840;  2),  Weeren  (1854;  i) 
and  Debray  ( 1855 ;  i )  have  also  studied  the  properties  of  beryl- 
lium hydroxide. 

Beryllium  Chlorate,  Bromate,  lodate,  and  compounds  of  beryl- 
lium with  oxygen  and  a  halide. 

Traube  (1894;  3)  gives  the  molecular  solution  volume  of 
Be(ClO3)2,  but  no  details  as  to  the  salt  itself.  Atterberg  (1873; 
7)  prepared  the  perchlorate,  Be(ClO4)2.4H2O,  and  a  periodate 
to  which  he  gave  a  very  improbable  formula.  He  could  not 
make  the  chlorate.  Marignac  (1873;  2)  tried  to  make  the  bro- 
mate  and  iodate  as  well,  but  obtained  only  indefinite  gummy 
masses.  He  states  further  that  the  perchlorate  only  takes  the 
crystalline  form  after  concentration  to  a  thick  syrup  and  is  very 
deliquescent.  Marignac  was  probably  the  nearest  correct  and  it 
is  doubtful  if  any  of  these  compounds  have  been  made  as  distinct 
individuals. 

Beryllium  Sulphates. — Six  normal  sulphates  of  beryllium  find 
place  in  chemical  literature : 

BeS04, 

BeSO4.H2O, 

BeSO4.2H2O, 

BeSO4.4H2O, 

BeS04.6H20, 

BeSO4.7H2O, 
of  which  the  heptahydrate  certainly  has  no  existence,  in  fact. 

Anhydrous  Beryllium  Sulphate,  BeSO4. — Nilson  and  Petters- 
son (1880;  9)  prepared  a  product  very  close  to  the  composition 
BeSO4  by  heating  the  dihydrate  at  250°.  The  sulphate  so  pre- 
pared had  a  specific  gravity=2.443  and  a  specific  heat=o.i978. 
Lebeau  (1896;  6,  1899;  u)  prepared  the  anhydrous  sulphate  by 
the  action  of  strong  sulphuric  acid  on  the  oxide  and  evaporation 
of  the  excess  of  acid.  Parsons  (1904;  10)  states  that  while 


30  CHEMISTRY    OF    BERYLLIUM 

the  product  obtained  by  either  of  the  foregoing  methods  is  un- 
doubtedly the  anhydrous  sulphate,  it  is  a  very  difficult  matter 
to  get  it  pure,  owing  to  the  fact  that  the  loss  of  the  last  trace 
of  water  on  heating  is  very  close  to  the  point  where  sulphur 
trioxide  begins  to  be  given  off  if  indeed  the  two  do  not  go  to- 
gether. Levi-Malvano  (1905;  7)  claims  that  this  is  a  mistake 
and  that  he  completely  eliminated  all  water  at  218°  to  220°. 

The  anhydrous  sulphate  is  stable  in  dry  air,  is  itself  insoluble 
in  water,  but  slowly  hydrates  and  goes  into  solution  as  the  tetra- 
hydrate.  It  loses  sulphuric  anhydride  even  below  a  red  heat, 
but  the  last  traces  are  only  driven  off  at  a  full  white  heat. 

Beryllium  Sulphate  Monohydrate,  BeSO4.H,O.— Levi-Malva- 
no (1905;  7)  claims  the  dihydrate  melts  at  158°  and  goes  over 
into  the  monohydrate. 

Beryllium  Sulphate  Dihydrate,  BeSO4.2H2O,  is  prepared  by 
drying  the  tetrahydrate  at  100°  and  is  stable  in  dry  air  below 
this  temperature.  Nilson  and  Pettersson  (1880;  6),  Kriiss  and 
Moraht  (1890;  7),  Parsons  (1904;  5,  1904;  10),  Levi-Malvano 
(1905;  7).  It  dissolves  readily  in  water  passing  back  into  the 
tetrahydrate. 

Beryllium  Sulphate  Tetrahydrate,  BeSO44H2O.— The  tetra- 
hydrate was  first  prepared  by  Berzelius,  (1815;  i)  who  con- 
sidered it  to  be  an  acid  salt.  Awdejew,  (1842;  2)  first  deter- 
mined its  true  character  and  used  the  salt  to  determine  the  atomic 
weight  of  beryllium.  It  was  also  employed  for  this  purpose 
by  Weeren  (1854;  i),  Klatzo  (1869;  i),  Nilson  and  Pettersson 
(1880;  6)  and  Kriiss  and  Moraht  (1890;  7).  Parsons  (1904;  5) 
showed  that  the  sulphate  lost  water  continuously  over  phosphoric 
anhydride  and  discarded  it  as  a  means  of  determining  the  atomic 
weight  of  the  element.  This  salt  of  beryllium  has  been  studied 
more  than  any  other  compound  of  the  metal. 

Preparation. — It  is  best  prepared  by  dissolving  beryllium  ox- 
ide, carbonate  or  hydroxide  in  excess  of  sulphuric  -acid,  evapo- 
rating in  platinum  and  heating  below  a  red  heat  until  the  larger 
part,  but  not  all,  of  the  white  fumes  of  sulphuric  acid  have 
been  driven  off,  dissolving  in  water,  evaporating  to  a  syrup  and 
turning  into  strong  95  per  cent,  alcohol.  By  this  procedure  a 


NORMAL    COMPOUNDS    OF    BERYLLIUM  3! 

milky  solution  is  produced  which  does  not  immediately  crystal- 
lize, but  after  a  few  hours  the  sulphate  will  have  almost  entirely 
separated.  To  insure  perfect  freedom  from  acid  two  more 
crystallizations  from  alcohol  are  necessary  and  the  salt  should 
finally  be  crystallized  from  water  to  insure  the  right  degree  of 
hydration.  The  salt  may  also  be  prepared  more  directly  and 
in  a  fair  state  of  purity  by  evaporating  the  sulphuric  acid  solu- 
tion to  dryness  and  heating  on  a  sand  bath  until  white  fumes 
cease  to  come  off,  taking  especial  care  not  to  use  too  high  a  tem- 
perature. The  anhydrous  sulphate  may  then  be  allowed  to 
stand  for  some  time,  with  occasional  stirring,  in  contact  with  cold 
\vater  filtered  and  the  solution  evaporated  to  crystallization. 

Properties. — Beryllium  sulphate  tetrahydrate  consists  of  color- 
less octahedral  crystals  belonging  to  the  tetragonal  system.  Ac- 
cording to  Topsoe  (1872;  i)  and  Topsoe  and  Christiansen  (1873; 
9)  the  crystals  are  unaxial  and  optically  negative.  Observed 
iorms  (on). (no);  a:c=i  10.9461.  Mean  indices  of  refraction 

C  =  1.4374  C  =  1.4691 

e     D  =1.4395  w      0=1.4720 

F  =  1.4450  F  =  1-4779 

Wulff  (1889;  4)  states  further  that  the  crystals  give  strong 
double  refraction.  Gladstone  and  Hibbert  (,1897;  6)  compared 
the  molecular  refraction  of  the  solid  sulphate,  47.41  with  the 
same  in  solution,  47.94.  Jahn  (.1891;  5)  found  the  specific 
rotation  for  the  sulphate  as  0.28895.  The  solution  friction  was 
studied  by  Wagner  (1890;  12).  Meyer  (1899;  3)  studied  the 
magnetic  susceptibility.  Traube  (1894;  3)  determined  the  molec- 
ular solution  volume.  Hober  (1898;  9)  found  that  the  sul- 
phate and  chloride  have  same  sweet  taste  at  equal  cation  con- 
centrations. According  to  Leys  (1899;  10)  and  Brunner  (1900; 
i)  the  sulphate  is  less  hydrolyzed  in  solution  than  the  sulphates 
of  aluminum  and  iron.  Brunner  gives  this  hydrolysis  in  N/4 
to  N/20  solution  as  0.52  per  cent,  to  0.68  per  cent.  According 
to  Weeren  (1854;  i)  the  crystals  lose  one-third  of  their  water 
of  crystallization  at  35°.  Parsons  (1904;  5)  by  tensimeter  ex- 
periments found  the  vapor  tension  of  the  crystals  at  20°  to  equal 
a  pressure  of  20  millimeters  of  olive  oil  and  to  increase  rapidly 


32  CHEMISTRY   OF   BERYLLIUM 

with  the  temperature.  Over  phosphoric  acid  the  crystals  lose 
water  slowly  at  ordinary  temperatures.  By  dissolving  one  mol 
BeSO4.4H2O  in  400  mols  of  water  Thomsen  (1873;  4)  found 
the  heat  of  solution  =-j-IIO°-  Pollok  (1904;  9)  gives  the  heat 
of  solution  as  o.85K°.  The  specific  gravity  has  been  determined 
as  follows:  Topsoe  (1872;  i)  (1873;  6)  1.725;  Nilson  and 
Fettersson  (1880;  9)  1.713;  Stallo  (Clark's  "Constants  of 
Nature")  1.6743  at  22°;  Kriiss  and  Moraht  (1890;  7)  1.7125. 

Beryllium  sulphate  tetrahydrate  is  soluble  in  about  its  own 
weight  of  water,  but  is  insoluble  in  absolute  alcohol.  Its  solu- 
tion is  strongly  acid  to  indicators,  attacks  zinc  with  evolution 
of  hydrogen  and  when  fully  concentrated  dissolves  two  equiva- 
lents of  its  own  hydroxide.  On  dilution  the  main  portion  of 
the  hydroxide  is  thrown  down,  but  approximately  one-half  of 
an  equivalent  remains  dissolved  at  infinite  dilution.  It  should 
be  crystallized  from  a  neutral  or  acid  solution,  for  although 
the  crystals  can  be  obtained  from  a  basic  solution  (1906;  5)  it 
is  impossible  to  separate  them  therefrom.  The  taste  of  the 
salt  is  a  mixed  acid  and  sweet. 

Beryllium  Sulphate  Hexahydrate. — Marignac  (1873;  i),  in  at- 
tempting to  repeat  Klatzo's  work  (1869;  i)  on  the  heptahydrate, 
after  many  attempts  obtained  only  once,  by  evaporating  a  super- 
saturated solution  of  sodium  sulphate  and  beryllium  sulphate,, 
a  mass  of  prismatic  crystals  which  he  thought  contained  six 
molecules  of  water.  They  immediately  effloresced  on  exposure 
to  air  and  could  not  have  been  the  hexahydrate  described  by 
Levi-Malvano  (1905;  7).  According  to  the  last  named  author 
he  obtained  crystals  of  the  hexahydrate  from  a  commercial 
source  and  after  repeated  trials  was  able  to  produce  the  salt  it- 
self by  treating  an  excess  of  but  a  little  diluted  sulphuric  acid 
with  enough  beryllium  hydroxide  or  carbonate  at  ordinary  tem- 
peratures to  insure  a  state  of  supersaturation  of  the  sulphate 
formed  and  suddenly  shaking  the  mass.  The  solution  itself 
should  contain  excess  of  acid,  and  inoculation  with  crystals  of 
the  hexahydrate  previously  produced  was  apparently  of  no  as- 
sistance. Crystallization  in  the  cold  did  not  seem  to  especially 
favor  the  formation  of  the  hexahydrate,  but  the  one  condition 


NORMAL    COMPOUNDS    OF    BERYLLIUM  33 

seemed  to  be  supersaturation.  Still  having  once  produced  the 
hexahydrate  it  could  be  crystallized  out  of  aqueous  solution  at 
temperatures  as  high  as  50°  and  he  even  threw  it  out  of  solu- 
tion at  90°  by  addition  of  boiling  alcohol.  On  the  other  hand 
when  at  — 30°  the  cryohydrate  was  reached,  the  hexahydrate 
was  present  mixed  with  ice.  According  to  Levi-Malvano  the 
hexahydrate  is  stable  in  air.  The  finely  pulverized  salt  melted 
at  78.8°,  but  on  removing  the  source  of  heat  and  cooling,  the 
solidification  point  of  the  syrupy  liquid  was  found  to  be  68.4°. 
This  was  probably  due  to  a  mixture  of  crystals  of  a  lower  hy- 
drate. The  solubility  curve  of  the  hexahydrate  which  is  given 
cuts  that  of  the  dihydrate  at  774°.  The  hexahydrate  on  igni- 
tion loses  water  and  yields  a  blue  oxide. 

Parsons  and  Fuller  (1906;  5)  made  many  attempts  to  produce 
the  hexahydrate,  but  without  success  and  think  that  some  con- 
dition besides  supersaturation  must  be  essential.  An  order  sent 
to  the  dealers  from  whom  Levi-Malvano  first  obtained  his  salt 
brought  a  bottle  labeled  "hexahydrate,"  but  which  on  examina- 
tion proved  to  be  nothing  but  the  regular  tetrahydrate. 

Beryllium  Sulphate  Heptahydrate.— Klatzo  (1869;  i)  thought 
he  had  produced  a  hydrate  with  seven  molecules  of  water  of 
crystallization.  His  work  is  unconfirmed  and  the  conditions 
which  he  gives,  would  in  themselves,  seem  to  render  its  produc- 
tion improbable,  if  not  impossible.  Parsons  (1904;  10)  states 
that  this  hydrate  undoubtedly  does  not  exist.  It  should  be  re- 
membered also  that  Marignac  (1873;  i)  found  Klatzo's  work 
to  be  incorrect  in  many  particulars. 

Beryllium  Sulphite,  BeSO3. — The  normal  salt  has  been  pro- 
duced only  by  Kruss  and  Moraht  (1890;  5)  who  prepared  it  by 
adding  freshly  precipitated  beryllium  hydroxide  wrhich  had  been 
dried  by  washing  with  alcohol,  to  alcohol  saturated  with  sulphur 
dioxide  and  evaporating  over  phosphoric  anhydride.  It  con- 
sists of  colorless  hexagonal  plates  which  are  immediately  de- 
composed by  water  yielding  sulphur  dioxide  and  beryllium  hy- 
droxide. For  several  so-called  basic  compounds  see  basic  salts. 
Atterberg  (1873;  7)  could  not  produce  a  sulphite. 
3 


34  CHEMISTRY   OF   BERYLLIUM 

Beryllium  Thiosulphite. — Factor  (1901 ;  5)  claims  to  have  pro- 
duced the  salt,  BeS2Q3.iiH2O,  by  the  action  of  a  solution  of 
sodium  thiosulphate  on  a  solution  of  beryllium  sulphate.  Some 
experiments  by  the  author  lead  him  to  believe  that  this  is  incorrect 
for  in  his  hands  an  admixture  of  these  two  solutions  always 
precipitates  sulphur  and  gives  off  sulphur  dioxide  as  was  to  be 
expected.  Marignac  (1875;  i)  and  Atterberg  (1873;  7)  could 
not  obtain  the  salt. 

Beryllium  Dithionate. — The  normal  salt  has  not  been  produced. 

Beryllium  Sulphocyanate,  Be(CyS)2. — Hermes  (1866;  2)  con- 
cluded that  the  somewhat  illy  denned  residue  obtained  by  the 
action  of  the  acid  on  beryllium  carbonate  was  the  sulphocyanate. 
Found  it  to  be  soluble  in  alcohol.  Toczynski  (1871;  2)  was 
unable  to  prepare  the  sulphocyanate  with  any  definiteness  and 
Atterberg  (1873 ;  7)  had  no  better  success. 

Beryllium  Selenate,  BeSeO44H2O. — Beryllium  selenate  was 
first  prepared  by  Atterberg  (1873;  7  and  8)  and  has  been  also 
studied  by  Topsoe  (1872;  i).  It  is  isomorphous  with  the  sul- 
phate and  like  the  sulphate,  loses  water  at  100°  forming  a  di- 
hydrate.  According  to  Topsoe  (1872;  i)  and  Topsoe  and 
Christiansen  (1873;  9),  it  crystallizes  in  the  rhombohedrai 
system,  a:b:c=i  :  0.9602  :  0.9027,  observed  forms  (on),  (101), 
(021),  (in),  (ooi).  Its  mean  indices  of  refraction  are 

Pa  V-b  PC 

C     1.4992  1-4973  1-4639 

D    1.5027  1.5017  1.4664 

F     1.5101  1.5084  i.4725 

Its  specific  gravity  (Topsoe)  is  2.029.  Roozeboom  (1891;  i) 
and  Topsoe  (1872;  i)  have  both  discussed  the  significance  of  the 
mixed  crystals  of  the  sulphate  and  selenate. 

Beryllium  Selenite,  BeSeO3-]-Aq. — Two  normal  selenites  find 
place  in  literature,  BeSeO3.H2O,  prepared  by  Atterberg  (1873; 
7)  and  BeSeO3.2H2O,  prepared  by  Nilson  (1875;  2). 
Nilson  states  that  his  salt  loses  one  molecule  of  water  at 
100°.  It  was  a  gummy  mass  decomposable  by  water  and  made 
by  evaporating  the  constituents  together.  Formula  arrived  at 
by  analysis  of  gummy  mass  and  no  evidence  of  individual  ex- 


NORMAL    COMPOUNDS    OF    BERYLLIUM  35 

istence.  Acid  selenites  (see  acid  salts)  and  so-called  basic 
selenites  (see  basic  salts)  have  been  prepared  in  much  the  same 
way.  None  of  these  salts  should  be  accepted  without  confirma- 
tion. 

Beryllium  Tellurates  and  Tellurites. — Berzelius  (1833;  2)  pre- 
cipitated beryllium  tellurate  and  tellurite  from  solution  by  means 
of  the  corresponding  potassium  salt.  They  were  obtained  as 
white  voluminous  flakes,  and  were  probably  basic  mixtures  but 
i;o  details  are  given. 

Beryllium  Chroniite,  BeCr2O4. — A  crystalline  compound  made 
by  Ebelmen  by  fusing  chromic  oxide,  beryllium  oxide  and  boric 
anhydride  together  and  treating  with  hydrochloric  acid.  De- 
scribed by  Mallard  (1887;  4). 

Beryllium  Chromate. — Atterberg  (1873;  7)  attempted  to  pro- 
duce a  neutral  chromate  but  was  not  successful.  The  author  of 
this  summary  and  his  students  have  repeatedly  attempted  to 
produce  a  chromate  of  definite  composition,  by  crystallizing  from 
aqueous  solutions  of  very  varied  acid  concentration  treated  with 
basic  carbonate,  to  all  degrees  of  saturation,  and  evaporated  both 
in  vacuo  and  in  the  air,  but  without  success.  If  chromic  acid 
was  present  in  excess  it  crystallized  out  first  and  no  separation 
of  another  definite  compound  could  be  obtained,  although  it  was 
of  course  a  simple  matter  to  obtain  residues  containing  any  de- 
sired ratio  between  the  beryllium  and  chromic  acid.  If  car- 
bonate was  added  to  saturation  or  even  in  excess  of  the  equiva- 
lent amount  and  long  before  the  solution  was  neutralized  only 
the  usual  indefinite  gummy  basic  chromates  were  obtained  on 
evaporation.  On  the  other  hand  Glassmann  (1907;  4)  claims 
to  have  made  a  neutral  chromate,  BeCrO4.H2O,  by  "neutraliz- 
ing" a  chromic  acid  solution  with  basic  carbonate  and  evaporat- 
ing, which  he  states  are  reddish  yellow  monoclinic  crystals,  de- 
composed by  water. 

Beryllium  Molybdate,  BeMoO3.2H2O. — prepared  by  Rosen- 
heim  and  Woge  (1897;  4)  by  boiling  equivalents  of  molybdic 
acid  and  beryllium  hydroxide  suspended  in  water.  An  oily  liquid 
layer  so  obtained  was  separated  in  a  separatory  funnel  and  after 
standing  two  weeks  in  the  cold  of  winter  solidified  to  an  aggre- 


36  CHEMISTRY   OF   BERYLLIUM 

gate  of  needle  like  crystals.  Analysis  shows  decided  basicity 
which  they  attribute  to  admixture  of  beryllium  hydroxide  im- 
possible to  remove. 

Beryllium  Nitrate. — The  normal  nitrate  was  an  article  of  com- 
merce before  it  found  place  in  literature.  Ordway  (1858;  I, 
1859;  2)  made  a  special  study  of  the  nitrates  and  found,  as  had 
been  the  case  with  Vauquelin  (1798;  5)  and  Gmelin  (1801;  i) 
that  they  are  extremely  difficult  to  crystallize.  By  precipitating 
a  solution  of  beryllium  sulphate  with  barium  nitrate  and  evap- 
orating the  solution  over  sulphuric  acid,  Ordway  produced  a 
solid  mass  that  approached  the  normal  nitrate  in  composition, 
but  still  basic  as  would  necessarily  result  from  any  method  in- 
volving the  presence  of  water  in  quantity.  Ordway  shows  how 
readily  the  nitrate  loses  nitric  anhydride  and  Parsons  (1904;  5) 
has  shown  that  by  evaporating  a  solution  of  the  nitrate  it  be- 
comes strongly  basic  below  50°,  and  on  slowly  drying  to  175° 
it  has  become  a  solid  which  has  already  lost  75  per  cent,  of  its 
nitric  anhydride.  Atterberg  (1873;  7)  could  make  no  nitrate. 

The  commercial  crystallized  nitrate,  which  can  be  obtained 
almost  perfectly  pure,  as  it  is  used  in  the  incandescent  mantle 
industry,  smells  strongly  of  nitric  anhydride,  melts  with  very 
little  heat  in  its  own  water  of  crystallization  and  immediately 
begins  to  show  bubbles  of  escaping  gas.  On  slowly  increasing 
the  heat,  the  nitric  anhydride  is  rapidly  evolved  leaving  behind 
a  viscous  glucose  like  mass,  which  is  still  readily  soluble  in 
water  when  it  has  reached  the  tribasic  condition.  Even  below 
175°  it  has  become  tetrabasic  and  loses  all  of  its  nitric  anhydride 
below  a  red  heat.  The  resultant  oxide  contains  a  small  amount 
of  occluded  oxygen  and  nitrogen,  which  if  the  decomposition  has 
been  gradually  brought  about,  is  equivalent  to  approximately 
0.35  cubic  centimeter  (Parsons,  1904;  5)  of  mixed  gases,  of 
which  approximately  two-thirds  are  nitrogen,  per  gram  of  oxide. 
The  nitrate  is,  of  course,  strongly  acid  in  reaction.  According 
to  Brunner  (1900;  i),  a  solution  of  the  nitrate  of  normality 
N/io  to  N/4O  is  hydrolyzed  from  1.8  per  cent,  to  1.9  per  cent. 

The  nitrate  is  easily  made  (1906;  13)  by  saturating  nitric  acid 
with  basic  beryllium  carbonate,  evaporating  to  a  syrupy  con- 


NORMAL    COMPOUNDS    OF    BERYLLIUM  37 

sistency,  adding  strong  nitric  acid  in  excess  and  crystallizing 
therefrom.  The  crystals  obtained  are  definite  in  composition 
and  have  the  composition,  Be(NO3)2.4H2O.  They  are  highly 
deliquescent,  lose  nitric  acid  readily,  and  are  stable  only  in 
presence  of  strong  nitric  acid  or  in  equilibrium  with  its  vapor. 
They  melt  in  their  own  water  of  crystallization  at  60.5  and  are 
soluble  in  alcohol  and  acetone. 

Beryllium  Nitrite. — Beryllium  nitrite  has  never  been  prepared. 
The  efforts  of  Vogel  (1903;  2)  proving  fruitless  as  the  solution 
immediately  hydrolyzed  with  loss  of  the  oxides  of  nitrogen.  It 
may  possibly  be  prepared  in  non-aqueous  solutions. 

Beryllium  Phosphate. — The  literature  of  the  normal  phosphates 
of  beryllium  is  very  far  from  clear,  as  the  few  investigators  who 
have  taken  up  the  matter  have  found  the  material  they  produced 
of  a  gelatinous  nature  and  difficult  to  identify  as  an  individual 
salt.  Sestini  (1890;  2),  by  boiling  an  acetic  acid  solution  of 
beryllium  phosphate,  obtained  a  flocculent  precipitate  to  which 
he  gave  the  formula,  Be3(PO4)2.3H2O-[-Aq.  Atterberg  (1873; 
7)  obtained,  by  adding  sodium  orthophosphate  to  a  soluble  beryl- 
lium salt,  a  flocculent  precipitate  to  which  he  assigned  the  for- 
mula, Be3(PO4)2.6H2O.  Prepared  by  precipitating  a  phosphoric 
acid  solution  of  beryllium  hydroxide  with  alcohol  it  contained 
7H20. 

Beryllium  Hypophosphate,  2BePO3-(-3H2O. — Rammelsberg 
(1891;  4)  .in  his  studies  of  the  hypophosphates  threw  down  a 
hot  solution  of  beryllium  sulphate  with  sodium  hypophosphace 
and  obtained  a  white  precipitate  having  the  composition,  2BePO3 
-h3H2O,  which  on  heating  to  23O°-25O°  lost  one-half  of  its 
water. 

Beryllium  Pyrophosphate,  Be2P2O7-5H2O. — By  precipitating  a 
solution  of  sodium  pyrophosphate  with  a  basic  solution  of  beryl- 
lium nitrate,  Scheffer  (1859;  3)  obtained  a  white  pulverulent  pre- 
cipitate which,  on  analysis,  yielded  results  close  to  the  theoreti- 
cal formula  for  the  pyrophosphate.  Atterberg  (1873;  7)  studied 
the  reaction,  but  did  not  identify  the  salt. 

Beryllium  Phosphite  and  Hypophosphite. — Rose  (1827;  i)  pre- 


38  CHEMISTRY   OF  BERYLLIUM 

cipitated  a  solution  of  beryllium  chloride  with  a  solution  of  phos- 
phorus trichloride  in  ammonia  and  again  (1828;  i)  saturated 
hypophosphorous  acid  with  beryllium  hydroxide,  obtaining  a 
gummy  mass.  Probably  neither  precipitate  was  the  normal  salt 
and  no  formula  was  -assigned. 

Beryllium  Vanadate. — Berzelius  (1831;  3)  in  his  researches 
on  the  vanadates  obtained  a  yellow,  neutral,  difficultly  soluble 
beryllium  vanadate  which  was  not  studied  and  to  which  no  for- 
mula was  assigned. 

Beryllium  Arsenate,  Be3(AsO4)2.6H2O. — Prepared  by  Atter- 
berg  (1875;  4).  Made  in  the  same  way  as  the  corresponding 
phosphate  which  it  resembled.  Almost  no  other  details. 

Beryllium  Antimonate,  Be(SbO3)2.6H2O. — This  salt  was  pre- 
pared by  Ebel  (1887;  2)  by  adding  a  soluble  beryllium  salt  to 
a  hot  solution  of  sodium  metantimonate. 

Beryllium  Columbate. — By  precipitating  beryllium  chloride  with 
potassium  columbate  and  fusing  the  precipitate  in  boric  anhydride 
Larsson  (1896;  10)  succeeded  in  obtaining  a  crystalline  colum- 
bate containing  6.24  per  cent.  BeO  and  89.60  per  cent.  Cb,O.;. 

Beryllium  Carbonate. — No  normal  carbonate  of  beryllium  is 
known.  The  carbonate,  BeCO3.4H2O,  claimed  by  Klatzo  (1869; 
i),  was  a  mistake  and  has  never  been  made,  and  can  not  be  made 
unless  from  non-aqueous  solution.  The  so-called  basic  carbon- 
ates are  important  and  several  double  carbonates  are  known  (see 
basic  salts  and  double  carbonates). 

Beryllium  Silicates. — The  work  on  the  normal  silicates  of 
beryllium  has  been  confined  to  the  artificial  production  of  a  meta 
silicate,  BeSiO3,  phenacite,  Be2SiO4,  and  beryl,  Be3Al2(SiO«)0. 
Phenacite  was  first  prepared  by  Ebelmen  (1887;  4)  by  fusing 
together  silicon  dioxide,  beryllium  oxide  and  borax  in  right  pro- 
portions. Later  Hautefeuille  and  Perrey  (1888;  4)  prepared  it 
by  fusing  SiO2  and  BeO  together  using  lithium  vanadate  and 
carbonate  as  a  mineralizing  agent,  and  still  later  (1890;  14,  and 
1893;  0  by  fusing  beryllium  sulphate  and  silicic  acid.  Beryl 
was  first  prepared  by  Williams  (1873;  3),  by  directly  fusing  to- 
gether its  constituents  and  later,  Hautefeuille  and  Perrey  (1888; 
4)  prepared  it  by  fusing  together  its  constituents  in  acid  lithium 


NORMAL    COMPOUNDS    OF    BERYLLIUM  39- 

molybdate.  Stein  (1907;  9)  by  fusing  in  a  carbon  tube  the  nec- 
essary quantities  of  BeO  and  SiO2  at  2000°  obtained  a  meta 
silicate,  BeSiO3  with  density  2.35  and  an  ortho  silicate  with  den- 
sity 2.46. 

Beryllium  Silicotungstate. — Wyrouboff  (1896;  i)  prepared  a 
crystalline  silicotungstate  to  which  he  gave  the  incomprehensible 
formula,  Be4(W12SiO40)3.93H2O,  when  c  ystallized  below  45°. 
Crystallized  above  45°  it  becomes  rhombohedral  with  87H2O. 
In  presence  of  nitric  acid  at  30°  a  45H2O  compound  is  obtained. 

Beryllium  Fluosilicate. — Berzelius  (1823;  i)  prepared  a  fluo- 
silicate  by  the  action  of  fluosilicic  acid  on  beryllium  hydroxide, 
but  did  not  analyze  or  give  details,  and  both  Atterberg  (1873 ;  7) 
and  Marignac  (1873;  i)  state  that  it  can  be  irrde  only  in  solu- 
tion. 

Beryllium  Aluminate,  Be(AlO2)2. — Occurs  in  nature  as  chryso- 
beryl  (cymophane,  alexandrite)  and  prepared  artificially  by  Ebel- 
men  (1851;  3)  by  fusing  theoretical  portions  of  alumina  and 
beryllia  in  boric  anhydrid  and  later,  by  Hautefeuille  and  Perrey 
by  fusing  a  mixture  of  the  oxides  of  aluminum  and  beryllium 
in  leucite  or  nephelite. 

Beryllium  Ferrocyanide  and  Ferricyanide. — Toczynski  (1871; 
2)  prepared  beryllium  ferrocyanide  by  adding  beryllium  sulphate 
to  barium  ferrocyanide  as  a  light  green  mass.  By  oxidizing 
with  chlorine,  he  obtained  the  ferricyanide  as  an  olive  green 
material.  Both  were  poorly  defined  and  probably  basic  in  nature 
as  Atterberg  (1873;  7)  has  pointed  out. 

Beryllium  Nitroprusside. — Toczynski  (1871;  2)  was  not  able 
to  prepare  a  nitroprusside. 

Beryllium  Methyl,  Be(CH3)2;  Beryllium  Ethyl,  Be(C2H5)2; 
Beryllium  Propyl,  Be(C3H7)2. — Beryllium  ethyl  was  first  pre- 
pared by  Cahours  (1860;  i)  by  the  action  of  metallic  beryllium 
on  ethyl  iodide  in  a  sealed  tube.  In  later  experiments,  (1873; 
i),  he  produced  enough  to  study  by  the  action  of  beryllium  on 
mercury  ethyl.  Found  it  to  be  a  colorless  liquid  boiling  at  185°- 
188°.  It  is  spontaneously  combustible  in  air  and  is  decomposed 
by  water.  It  can  be  distilled  in  an  atmosphere  of  carbon  diox- 
ide. Beryllium  propyl  was  also  prepared  by  Cahours  (1873;  i) 


40  CHEMISTRY   OF   BERYLLIUM 

in  a  similar  manner  by  the  action  of  beryllium  on  mercury  pro- 
pyl  in  a  sealed  tube  at  I3O°-I35°.  It  was  also  a  liquid  boiling 
at  244°-246°  with  properties  similar  to  beryllium  ethyl. 

Beryllium  methyl  was  later  prepared  by  Lavroff  (1884;  3)  m 
a  similar  manner  by  the  action  of  metallic  beryllium  on  mercury 
methyl  in  a  sealed  tube  at  130°.  It  is  a  white  volatile  crystalline 
substance  decomposed  by  water  with  evolution  of  light,  into 
methane  and  beryllium  hydroxide. 

Beryllium  Formate,  Acetate,  Propionate,  Etc. — Although  many 
attempts  were  made  by  Vauquelin  (1798;  5),  Urbain  and  Lacombe 
(1901  ;2, 190253)  and  others,  no  normal  salt  of  beryllium  with  any 
member  of  the  fatty  acids  was  made  until  Steinmetz  (1907;  5) 
finally  succeeded  in  preparing  the  normal  acetate,  Be(C2H3O2)2, 
by  heating  equal  parts  of  basic  acetate,  Be4O(C2H3O2)6,  and 
glacial  acetic  acid  with  five  to  six  parts  of  acetic  anhydride  for  two 
hours  in  a  sealed  tube  at  140°.  He  obtained  under  these  con- 
ditions crystals  of  the  normal  acetate,  as  small  double  refracting 
leaflets,  which  were  insoluble  in  water,  alcohol,  ether,  and  other 
organic  solvents.  They  melted  with  decomposition  at  300°  yield- 
ing a  sublimate  of  the  basic  acetate.  They  were  also  slowly  hy- 
drolyzed  by  boiling  water. 

Tanatar  (1907;  12)  claims  to  make  the  normal  formate, 
Be(CHO2)2,  by  slowly  evaporating  over  sulphuric  acid  a 
solution  of  formic  acid  neutralized  with  the  basic  carbonate. 
He  also  claims  to  make  the  basic  formate,  Be4O(CHO2)6,  by 
mixing  the  calculated  weights  and  boiling  in  water.  While  it  is 
a  simple  matter  to  get  a  mass  under  these  conditions  that  will 
give  almost  any  desired  per  cent,  of  BeO,  which  was  his  appar- 
ent criterion,  anyone  familiar  with  the  real  properties  of  the 
element  would  know  that  neither  of  these  salts  could  possibly 
be  made  under  these  conditions.  Tanatar  apparently  did,  how- 
ever, make  the  normal  propionate,  Be(C3H5O2)2,  by  heating,  at 
150°,  the  basic  propionate  with  propionic  acid  mixed  with  it:; 
anhydrid.  It  is  little  affected  by  solvents  as  Steinmetz  (1907; 
5)  found  to  be  the  case  with  the  acetate. 

Beryllium  Acetylacetonate,  Be(C0H7O2)2. — Beryllium  acetyl- 
acetonate  is  one  of  the  most  interesting  of  the  salts  of  beryllium. 
It  was  first  prepared  by  Combes  (1894;  6)  by  the  action  of 


NORMAL   COMPOUNDS   OF   BERYLLIUM  4! 

acetylacetone  on  a  solution  in  equivalent  quantities  of  beryllium 
hydroxide  in  acetic  acid.  He  found  it  to  be  a  white  crystal- 
line solid  melting  at  108°,  easily  sublimed,  and  boiling  at  270°. 
Two  determinations  of  its  vapor  density  showed  its  molecular 
weight  to  correspond  with  the  formula,  Be(C5H7O2)2.  Parsons 
(1904;  5)  who  used  this  salt  as  a  basis  in  his  atomic  weight 
determinations  made  a  careful  study  of  the  compound.  He 
found  it  to  be  most  readily  prepared  by  the  direct  action  of 
acetylacetone  on  basic  beryllium  carbonate  or  hydroxide.  Accord- 
ing to  this  author,  the  specific  gravity  of  beryllium  acetylaceton- 
ate  is  1.168  compared  to  water  at  4°.  It  is  a  perfectly  white  crys- 
talline substance  which  is  slightly  soluble  in  cold  water,  more 
soluble  in  hot  water  and  slowly  hydrolyzed  by  boiling  water 
with  loss  of  acetylacetone  and  precipitation  of  beryllium  hydrox- 
ide. It  is  readily  soluble  in  alcohol  and  is  easily  crystallized 
therefrom  in  rhombic  plates.  It  is  soluble  in  benzene,  toluene, 
xylene,  naphtha,  and  all  petroleum  distillates,  chloroform,  tur- 
pentine, methyl  alcohol,  amyl  alcohol,  ether,  ethyl  acetate,  ace- 
tone and  carbon  disulphide.  It  sublimes  many  degrees  below 
its  boiling  point  and  begins  to  sublime  even  below  the  boiling 
point  of  water.  The  sublimed  crystals  are  light  and  flocculent 
with  a  marked  resemblance  to  flakes  of  snow.  It  is  soluble  in 
acids  setting  free  acetylacetone. 

Beryllium  Oxalate  Trihydrate,  BeC2O4.3H2O.— Although  early 
attempts  were  made  by  Vauquelin  (1798;  5),  Debray  (1855;  i) 
and  Atterberg  (1873;  /)  to  produce  the  normal  oxalate,  they 
were  not  successful  and  it  was  first  made  by  Rosenheim  and 
\\oge  (1897;  4).  \Vyrouboff  (1902;  i)  confirms  the  results 
of  Rosenheim  and  Woge,  and  Parsons  and  Robinson  (1906;  i) 
made  a  study  of  the  system,  BeO  :C2O3  :H,O,  also  producing  the 
normal  oxalate.  All  three  authors  produced  their  oxalate  by 
adding  basic  beryllium  carbonate  or  hydroxide  to  excess  of  oxalic 
acid  and  crystallizing  the  oxalate  therefrom.  It  was  found  al- 
most impossible  to  get  the  salt  absolutely  free  from  excess  of 
oxalic  acid  by  crystallization  and  to  procure  the  perfectly  neu- 
tral salt.  Parsons  and  Robinson  added  the  necessary  measured 
quantity  of  beryllium  basic  carbonate.  Any  excess  of  base  pre- 


42  CHEMISTRY   OF   BERYUJUM 

vented  crystallization.  The  crystals  of  the  trihydrate  were  de- 
scribed by  Wyrouboff  (1902;  i).  The  crystals  were  figured  in 
the  article  of  Parsons  and  Robinson  and  the  measurements  made 
by  Penfield  and  Heath  ( 1906 ;  I )  showed  the  crystals  to  be  ortho- 
rhombic.  The  forms  observed  c(ooi),  d(ioi),  p(in).  The 
angles 

P  AP'",  in  A  iii  =  74°i6' 

PAP,     inAin  =  9o06' 

CAP,     ooi  A  in  =  68°3o' 

Calculated  68°2o/ 

The  first  two  measurements  yielded  the  axial  ratio  a  :b  :<:= 
0.853  :  i.o  :  1.645.  ^T°  distinct  cleavage  was  observed.  The  c 
axis  is  a  bisectrix  and  the  plane  of  the  optical  axis  is  the 
brachypinacoid.  In  the  crystal  examined,  the  interference  fig- 
ure was  indistinct  and  the  axial  angle  so  large  that  the  hyper- 
bolas opened  out  beyond  the  field  of  view. 

Beryllium  oxalate  trihydrate  is  stable  at  room  temperature. 
It  is  soluble  in  less  than  its  own  weight  of  boiling  water  and  is 
but  little  less  soluble  at  ordinary  temperatures.  It  is  strongly 
acid  in  reaction  and  in  concentrated  solution  dissolves  1.85  equiv- 
alents of  its  own  carbonate  or  hydroxide.  It  has  a  sharp  sweet- 
ish taste.  Heated  at  100-105°  it  loses  two  thirds  of  its  water 
of  crystallization  forming  the  monohydrate. 

Beryllium  Oxalate  Monohydrate. — Prepared  by  Rosenheim  and 
Woge  (1897;  4)>  Wyrouboff  (1902;  i)  and  by  Parsons  and 
Robinson  (1906;  i).  Is  made  by  heating  the  trihydrate  at 
100-105°.  Heated  much  above  this  temperature  it  begins  to  lose 
water,  at  first  slowly,  but  more  rapidly  as  the  thermometer 
reaches  220°,  at  which  temperature  the  oxalate  begins  to  de- 
compose and  at  350°  is  completely  converted  into  the  oxide. 

Beryllium  Tartrate,  BeC4H4O6+3H2O.— Vauquelin  (1898;  5) 
and  Toczynski  (1871 ;  i)  attempted  the  production  of  the  normal 
tartrate,  but  it  was  first  reported  by  Atterberg  who  gave  to  it 
the  formula,  BeC4H4O6-f  3H2O.  Atterberg  gives  few  details, 
but  the  salt  is  confirmed  by  Rosenheim  and  Itzig  (1899;  15)  who 
simply  state  the  fact.  The  chief  characteristic  of  the  tartratcs. 
of  beryllium  and  a  fact  which  gives  them  especial  interest  is 


NORMAL  COMPOUNDS  OF   BERYLLIUM  45 

their  abnormally  great  rotatory  power.  This  fact  was  first 
brought  out  by  Biot  (1838;  i)  on  a  tartrate  of  unstated  com- 
position prepared  by  Berthier,  who  found  the  beryllium  tartrate 
to  have  the  largest  specific  rotatory  power  of  any  tartrate  ex- 
amined, viz.,  in  100  millimeters  +41.134  to  +43.992.  Rosenheim 
and  Itzig  (1899;  13)  in  their  work  on  some  double  tartrates, 
(which  see)  confirm  this  fact  and  found  the  rotation  of  polar- 
ized light,  both  right  and  left,  was  greatly  increased  by  the  in- 
corporation of  beryllium  in  the  molecule.  By  saturating  tar- 
taric  acid  with  freshly  precipitated  beryllium  hydroxide  at  boil- 
ing heat  and  evaporation,  they  obtained  a  basic  uncrystallizable 
glassy  mass  whose  analysis  led  to  the  formula,  Be3C4H2O7+7H2O, 
which  had  a  very  high  rotatory  power,  their  four  experiments 
giving  [M J^-j- 171°  to  +176.8°.  The  rotatory  power  showed 
a  change  on  dilution  owing  to  hydrolysis  and  the  authors  were 
inclined  to  believe  they  had  here  a  beryllium  salt  of  diberyllium 
tartrate,  similar  to  potassium  diberyllium  tartrate,  to  be  described 
later. 

Beryllium  Succinate,  BeC4H4O4+2H2O.— Atterberg  (1893; 
7)  obtained  this  salt  by  dissolving  the  hydrate  or  carbonate 
in  excess  of  succinic  acid  and  concentrating  at  a  thick  syrup 
fiom  which  small  crystals  separated.  These  crystals  lost  their 
water  of  crystallization  at  100°.  They  are  only  stable  in  pres- 
ence of  an  excess  of  succinic  acid. 

Beryllium  Picrate. — Lea  (1858;  2)  reports  a  golden  yellow 
crystalline  picrate  made  by  dissolving  basic  beryllium  carbon- 
ate in  picric  acid.  No  analysis,  and  it  was  probably  basic. 
Glassmann,  (1907;  6)  by  "neutralizing"  picric  acid  solution  with 
basic  beryllium  carbonate  obtained  yellow  scales  which  he  dried  in 
the  air  and  assigned  the  formula,  Be  (C6H2O7N3)2.3H2O.  By  wash- 
ing with  ether,  he  dried  it  somewhat  and  assigned 
Be(C6H2O7N3)2.2H2O  to  the  product,  and  since  by  drying  at 
I2O°-I3O°  he  obtained  a  product  which  gave  a  molecular  lowering- 
in  acetophenone  corresponding  to  465  and  a  BeO  content  nearly 
theoretical,  he  assumed  he  had  anhydrous  Be(C6H2O7.N3),2. 
He  apparently  measured  his  lowering  only  to  the  second  decimal 
and  a  slight  error  would  have  given  a  very  different  result, 


44  CHEMISTRY    OF    BERYLLIUM 

especially  as  it  has  been  shown  (1907;  10)  that  dissolving  beryl- 
lium hydroxide  in  solutions  of  its  normal  salts  raises  the  freezing 
point,  if  he  obtained  a  "neutral"  solution  these  are  the  only 
conditions  that  could  have  prevailed.  As  he,  himself,  claims 
that  water  (in  which  it  was  made)  decomposes  the  picrate  and 
as  oxide  content  is  no  criterion  of  composition,  especially  with 
beryllium  salts,  his  results  need  confirmation  before  being  ac- 
cepted. 

Beryllium  Alpha  Brom  Camphor  Sulphonate,  Be(C10H14BrO. 
SO2.O)2,  was  prepared  by  Walden  (1894;  7)  and  although  he 
gives  no  detail  of  the  salt  itself,  he  studied  its  optical  rotation 
m  comparison  with  the  analogous  magnesium,  zinc  and  barium 
salt  in  dilute  solution  and  found  for  same  molecular  concentration 
essentially  the  same  rotation.  Concluded  that  the  beryllium 
ions  were  therefore  inactive.  Biot  (1838;  i)  and  Rosenheim 
and  Itzig  (1899;  13)  would  seem  to  be  led  to  a  contrary  conclu- 
sion in  the  case  of  the  tartrate  unless,  as  indeed  Rosenheim  and 
Itzig  indicate,  a  complex  ion  is  formed. 

Beryllium  Rhodizonate,  Be(H2C3O5)  ;  Beryllium  Kroconate, 
Be(HC5O4).— Two  substances  reported  by  Heller  (1837;  i). 
The  first  was  a  brown  powder  and  the  second  yellow  crystals. 
Both  made  by  treating  an  alcoholic  solution  of  the  correspond- 
ing acid  with  beryllium  acetate. 

Beryllium  Citraconate,  BeC5H4O4 ;  Beryllium  Fumarate,  Beryl- 
lium Maleate,  BeC4H2O4. — Have  no  basis  for  a  claim  to  existence 
except  the  BeO  content  of  a  substance  made  by  Tanatar  (1907; 
12),  b>f  treating  the  corresponding  acid  with  basic  carbonate  and 
evaporating.  There  is  nothing  to  indicate  that  they  are  not  the 
usual  indefinite  basic  mixtures  obtained  under  these  conditions. 


CHAPTER   IV 


ACID  SALTS  OF  BERYLLIUM. 

Beryllium  has  very  little  tendency  to  form  acid  salts  and  only 
an  acid  oxalate,  an  acid  molybdate,  an  acid  phosphate,  an  acid 
arsenate  and  four  acid  selenites  have  place  in  chemical  litera- 
ture. The  first  has  been  shown  to  be  a  simple  mixture  of  the 
normal  oxalate  and  oxalic  acid,  and  the  molybdate  and  selenites 
were  little  more  than  the  residues  left  on  evaporating  the  con- 
stituents with  little  of  detail  in  their  study.  The  phosphate 
was  non-crystalline.  These  salts  need  confirmation  although 
from  the  well  known  tendencies  of  phosphoric  acid,  the  existence 
of  an  acid  phosphate  would  seem  as  probable  as  any  acid  salt  of 
beryllium. 

Beryllium  Monoacid  Phosphate,  BeHPO4.3H2O.— Sheffer 
(T859;  3)  precipitated  a  nitric  acid  solution  of  beryllium  with 
disodium  acid  phosphate,  obtaining  a  white  non-crystalline  pow- 
der, and  gave  the  formula,  BeHPO4.3H2O,  to  the  precipitate 
formed.  He  found  it  lost  two  molecules  of  water  on  drying. 
Atterberg  ( 1875 ;  4)  also  obtained  the  same  substance  by  solu- 
tion of  the  hydroxide  in  phosphoric  acid  and  precipitating  with 
alcohol.  A  viscous  mass  was  obtained  which  analyzed  near  to 
the  above  formula.  By  dissolving  in  phosphoric  acid  and  pre- 
cipitating with  alcohol,  Sheffer  thought  the  mass  formed  had 
the  composition,  5BeO.2P,O54H2O. 

Beryllium  Acid  Arsenate,  BeHAsO4.2H2O. — Reported  by  At- 
terberg (1875;  4)  as  resembling  the  corresponding  phosphate 
and  made  in  the  same  way. 

Beryllium  Acid  Selenites. — Nilson  (1875;  2.  and  1875;  3)  re- 
ported four  beryllium  selenites  apparently  acid  in  nature,  Be- 
SeO3.H2SeO3,  BeSeO3.2H2SeO3,  5BeO.8SeO2.5H2O  and  3BeO. 
7SeO2.5H2O.  Whether  these  substances  are  mixtures  or  def- 
inite individuals  needs  confirmation,  as  they  were  little  more 
than  the  residues  left  on  evaporating  the  constituents  together. 


46  CHEMISTRY   OF   BERYLLIUM 

Atterberg  (1873;  7)  did  not  succeed  in  making  any  acid  selen- 
ites,  although  he  obtained  the  usual  basic  mixture. 

Beryllium  Acid  Oxalate. — Rosenheim  and  Woge  (1897;  4)  re- 
ported the  compound,  2BeC2O4.H2C2O4.5H2O.  This  was  in- 
vestigated by  Parsons  and  Robinson  (1906;  i)  who  showed 
that  the  substance  is  simply  a  mixture  of  the  normal  oxalate 
and  oxalic  acid.  All  attempts  to  make  it  as  a  distinct  substance 
met  with  failure. 

Beryllium  Acid  Molybdate. — Atterberg  (1873;  7)  reported  an 
acid  molybdate,  BeMoO4-f  MoO3+ xAq,  but  gives  little  detail. 


CHAPTER  V 


DOUBLE  SALTS  OF  BERYLLIUM.1 

Many  well  defined  and  crystalline  double  salts  of  beryllium 
have  been  made.  In  many  cases  the  double  salts  are  readily 
prepared  and  are  quite  stable  when  the  normal  single  salt  can 
not  be  produced  at  all  or  only  in  the  absence  of  water.  This  is 
notably  true  in  the  case  of  the  double  carbonates,  chlorides,  io- 
dides, nitrites  and  sulphites.  In  general  these  salts  have  been 
but  little  studied,  their  discoverers  being  content  with  their 
identification  and  analysis.  Being  less  subject  to  the  confusing 
action  of  hydrolysis  than  either  the  normal  or  basic  salts  of 
beryllium,  their  description  and  identity  can,  as  a  rule,  be  de- 
pended upon  when  found  in  literature. 

DOUBLE  CHLORIDES. 

Potassium  Beryllium  Chloride,  BeCl2.2KCl. — Enumerated  by 
H.  L.  Wells  (1901;  3)  in  his  list  of  double  halides.  Authority 
has  not  been  found.  Welkow  (1874;  6)  could  not  obtain  a 
double  chloride  with  either  potassium  or  sodium. 

Mercury  Beryllium  Chloride,  2BeCl2.3HgCl2-f-6H2O.— A  double 
chloride  with  mercury  has  been  reported  by  two  observers, 
Hrst  by  Bonsdorff  (1828;  4)  who  simply  states  it  was  obtained 
in  rhombic  prisms,  but  gives  no  analysis  or  formula,  and  second 
by  Atterberg  (1873;  7)  who  obtained  it  in  large  tabular  hydro- 
scopic  crystals  by  evaporation  of  like  equivalents  of  the  two 
chlorides  in  excess  of  strong  hydrochloric  acid.  Marignac 
(1873;  i)  could  not  obtain  the  double  salt  and  states  that  it  is 
a  mistake  and  the  HgCl,  crystallizes  out  alone. 

Auric  Beryllium  Chloride,  BeCl2.AuCl3  and  BeCl2.2AuCl3.— 
Obtained  by  Atterberg  (1873;  7)  together  from  a  solution  of 
like  equivalent,  allowed  to  stand  for  a  long  time  over  sulphuric 
acid.  The  first  crystallized  as  tetragonal  double  pyramids  and 
iater  the  crystals  of  the  second  form  settled  out. 

1  Some  salts  are  included  here  which  are  possibly  not  true  double  salts 
but  salts  of  a  complex  acid. 


4  CHEMISTRY   OF   BERYUJUM 

Stannic  Beryllium  Chloride,  BeCl2.SuCl4.8H2O.  — -  Atterberg 
(^73  >  7)>  by  dissolving  tin  chloride  and  beryllium  oxide  in 
excess  of  hydrochloric  acid  and  evaporating  over  sulphuric  acid, 
obtained  some  ill  defined  rhombic  pyramids.  They  deliquesced 
easily  in  air.  Marignac  (1873;  i)  was  not  able  to  obtain  any 
double  salt  with  tin. 

Ferric  Beryllium  Chloride,  BeCL.FeCl3+H2O.— Orange  yel- 
low crystals  obtained  by  adding  beryllium  chloride  to  warm 
concentrated  hydrochloric  acid  (1.19  specific  gravity)  to  which 
a  large  amount  of  ferric  chloride  had  already  been  added  and 
allowing  the  solution  to  cool.  Neumann  (1888;  i). 

Chromic  Beryllium  Chloride,  BeCl2.CrCl3.H2O. — Prepared  as 
violet  hydroscopic  crystals  by  Neumann  (1888;  i)  by  dissolv- 
ing chromic  chloride  in  strong  alcohol,  adding  some  beryllium 
chloride  and  passing  hydrochloric  acid  gas  through  the  heated 
mixture. 

Thallic  Beryllium  Chloride,  3BeCl2.Tl2Cl6.  —  By  dissolving 
thallium  oxide  and  beryllium  chloride  in  strong  hydrochloric  acid 
and  oxidizing  with  chlorine,  Neumann  (1888;  i)  obtained 
rhombic  tabular  crystals  of  the  above  formula. 

lodic  Beryllium  Chloride,  BeCl2.2lCl3.8H,O.— Obtained  by 
Weinland  and  Schlegelmilch  by  passing  a  current  of  chlorine 
through  a  cold  strong  hydrochloric  acid  solution  of  beryllium 
chloride  to  which  an  excess  of  iodine  had  been  added.  Gold 
yellow  needles,  very  unstable  and  hydroscopic. 

Platinous  Beryllium  Chloride,  BeCl2.PtCl2.5H2O.  —  Nilson 
(1876;  2)  prepared  the  beryllium  chlorplatinate  by  evaporating 
together  platinum  dichloride  and  beryllium  chloride  in  hydrochlo- 
ric acid  solution.  Obtained  dark  red  crystals  soluble  in  water, 
which  at  100°  lost  both  water  and  hydrochloric  acid. 

Platinic  Beryllium  Chloride,  BeCl2.PtCl4.8H,O.— First  pre- 
pared by  Thomsen  (1870;  i)  by  dissolving  beryllium  hydroxide 
in  a  hydrochloric  acid  solution  of  platinic  chloride  and  crystal- 
lizing. Thomsen  assigned  9H2O,  but  was  corrected  by  Marig- 
nac (1873;  3).  Further  by  heating  at  120°,  he  found  his  crys- 
tals lost  water  and  then  had  the  composition,  BeCl2.PtCl4.4H2O. 
It  was  later  prepared  by  Welkow  (1873;  5).  The  crystals  are 


DOUBLE   SALTS  OF  BERYLLIUM  49 

dark  yellow  or  orange,  four,  six,  or  eight-sided  prisms,  soluble 
in  alcohol  and  very  hydroscopic. 

Palladous  Beryllium  Chloride,  BeCl2.PdCl2.6H2O.— Welkow 
(1874;  6),  by  heating  a  concentrated  solution  of  beryllium  pal- 
ladic  chloride,  caused  it  to  lose  chlorine  and  obtained  brown 
tabular,  hydroscopic  crystals  having  the  above  formula  and 
readily  soluble  in  water  and  alcohol. 

Palladia  Beryllium  Chloride,  BeCl2.PdCl4.8H,O.— Obtained  by 
Welkow  (1874;  3)  as  small,  dark,  reddish  brown,  quadratic 
tables  by  evaporating  a  solution  of  the  constituents  over  sulphur- 
ic acid.  It  is  isomorphous  with  the  corresponding  platinum 
salt,  but  loses  all  of  its  water  at  130°. 

DOUBLE  FLUORIDES. 

Potassium  Beryllium  Fluoride,  BeF2.KF  and  BeF2.2KF.—  Two 
double  fluorides  of  potassium  are  known.  The  second  of  these 
was  produced  as  early  as  1811  by  Gay  Lussac  and  Thenard 
and  again  in  1823  by  Berzelius,  but  they  made  no  analyses. 
Awdejew  (1842;  2)  prepared  and  studied  BeF2.2KF  and  Debray 
(1855;  i),  BeF2.KF.  Gibbs  (1864;  3),  Marignac  (1873;  2), 
and  finally  Lebeau  (1898;  8,  1899;  n)  confirmed  the  salts  and 
Marignac  fully  described  the  crystals  of  BeF2.2KF,  but  the  other 
salt  yielded  no  well  defined  crystals.  Crystals  of  BeF2.2KF  are 
readily  thrown  down  by  evaporation  of  a  mixture  of  the  constitu- 
ents. It  is  soluble  in  19  parts  of  boiling  water  and  50  parts  of 
water  at  20°.  It  decrepitates  slightly  when  heated  and  fuses 
at  a  red  heat.  If  large  excess  of  BeF2  is  present,  a  mass,  hav- 
ing approximate  composition,  BeF2.KF,  is  formed,  which  on  be- 
ing again  crystallized  yields  the  first  named  salt.  Its  individ- 
uality as  a  definite  double  salt  seems  somewhat  doubtful.  Klatzo 
(1869;  i)  claims  these  salts  can  not  be  made,  but  Lebeau  (1899; 
n)  confirms  Marignac. 

Sodium  Beryllium  Fluorides,  BeF2.NaF,  BeF2.2NaF.— Two 
sodium  beryllium  fluorides  have  been  described  by  Marignac 
(1873;  2)  and  Lebeau  (1899;  n),  entirely  analogous  to  the 
potassium  salts.  They  were  made  in  a  similar  way  by  the  simple 
evaporation  of  their  constituents,  and  again  it  is  the  disodium 
salt  that  is  obtained  most  easily  and  in  definite  crystals.  BeF2. 
4 


5O  CHEMISTRY   OF   BERYLLIUM 

2NaF  is  easily  obtained  by  evaporation  in  small,  hard,  brilliant 
dimorphous  crystals,  both  forms  of  crystals  being  rhombohedral 
prisms,  but  of  different  angle.  The  salt  is  soluble  in  68  parts 
of  water  at  18°  and  in  34  parts  at  100°.  Marignac  gives  draw- 
ings and  measurements  of  the  crystals  of  BeF2.2NaF  and  could 
get  no  definite  crystals  of  the  other  salt,  which  like  the  corre- 
sponding potassium  compound,  seems  to  be  of  doubtful  existence 
as  a  definite  compound. 

Ammonium  Beryllium  Fluoride,  BeF2.2NH4F. — First  prepared 
by  Marignac,  (1873;  2)  and  later  studied  by  v.  Helmholt  (1893; 
2)  and  Lebeau  (1899;  n).  Obtained  by  evaporating  the  con- 
stituents as  small  colorless  needles  or  rhombic  prisms.  It  is 
isomorphous  with  the  corresponding  potassium  salt.  Lebeau 
used  it  as  a  means  to  prepare  pure  beryllium  fluoride.  Marignac 
figures  the  crystals  and  gives  full  measurements. 

DOUBLE  IODIDES. 

Welkow  (1874;  6)  obtained  a  double  iodide  of  beryllium 
-with  bismuth  and  one  with  antimony,  but  was  unable  to  separate 
them  from  the  mother  liquors  and  identify  the  salts. 

Mosnier  (1897;  7)  produced  a  double  beryllium  lead  iodide 
l)y  saturating  a  hydriodic  acid  solution  of  beryllium  iodide  with 
lead  iodide.  He  obtained  fine  yellow  needles  decomposed  by 
-water,  the  analysis  of  which  agreed  fairly  well  with  the  formula, 
13eI2.PbI2.3H2O,  although  Mosnier  preferred  to  consider  beryl- 
lium as  a  triad. 

DOUBLE  SULPHIDES. 

Berzelius  (1826;  2)  reported  a  double  sulphide  with  tungsten 
but  did  not  identify  the  salt. 

DOUBLE  CYANIDES. 

Beryllium  Platinum  Cyanide,  BePtCy44H2O. — Toczynski 
(1871;  2)  made  beryllium  platino  cyanide  in  gold  yellow  crys- 
tals by  the  action  of  beryllium  sulphate  on  barium  platino  cy- 
anide and  crystallization  from  alcohol.  Atterberg  (1873;  7) 
confirmed  his  results.  By  mixing  this  with  the  corresponding 
magnesium  salt  and  recrystallizing,  Toczynski  obtained  crys- 
tals to  which  he  assigned  the  formula,  BeMg2Pt3Cy1..4-i6H2O. 


DOUBLE  SALTS  OF  BERYLLIUM  51 

Beryllium  Platibromo  Cyanide,  BePtBr2(Cy)4. — Obtained  by 
Holtz  (1873;  10)  as  thin  plates. 

DOUBLE  SULPHATES. 

Beryllium  Potassium  -Sulphate,  BeSO4.K2SO4.2R,O.— This 
sulphate  was  probably  first  prepared  by  Vauquelin  (1798;  2), 
but  was  first  described  by  Awdejew  (1842;  2)  and  later  by 
Debray  (1855;  i),  Klatzo  (1869;  i),  Marignac  (1873;  2)  and 
Atterberg  (1873;  7),  all  of  whom  agree  essentially  as  to  formu- 
la and  details.  It  is  prepared  by  the  simple  evaporation  of 
its  constituents  in  like  proportions.  The  crystals  are  small  and 
colorless  and  even  Marignac  was  unable  to  determine  their  form. 
They  are  much  more  soluble  in  hot  than  in  cold  water.  Klatzo 
thought  they  contained  3H2O  when  crystallized  between  — 2  and 
-3°  C. 

Beryllium  Acid  Potassium  Sulphate,  BeSO4.K2SO4.2HKSO4. 
4H2O. — Atterberg  (1873;  7)  by  evaporating  a  strongly  acid  so- 
lution of  like  equivalents  of  beryllium  sulphate  and  potassium 
sulphate,  obtained  a  mass  of  fine  needle-shaped  prisms  to  which 
he  assigned  the  above  formula. 

Sodium  Beryllium  Sulphate,  3BeSO4.2Na2SO4.i2H,O.  —  Re- 
ported by  Atterberg  (1873;  7)  as  fine  needle-shaped  crystals 
forming  in  radiating  star-shaped  groups  and  obtained  by  evapo- 
rating a  solution  containing  three  equivalents  of  beryllium  sul- 
phate and  one  of  sodium  sulphate,  to  a  thick  syrup.  Loses 
7H2O  at  100°. 

Ammonium  Beryllium  Sulphate,  BeSO4.(NH4)2SO4.2H2O. - 
Obtained  by  Atterberg  (1873;  7)  by  evaporating  like  equiva- 
lents of  the  two  sulphates  first  by  heat  and  then  over  sulphuric 
acid  to  a  thick  syrup.  On  stirring,  the  syrup  became  a  crys- 
talline mass  and  by  pouring  out  the  mother  liquor,  he  obtained 
the  crystals  to  which  he  assigned  the  above  formula.  They  lost 
all  their  water  at  110°. 

DOUBLE  SULPHITES. 

Potassium  Beryllium  Sulphite,  2BeSO3.K2SO3.9H,O. — Rosen- 
heim  and  Woge  (1897;  4J  obtained  this  salt  in  the  crystalline 
form  by  saturating  acid  potassium  sulphite  with  beryllium  hy- 
droxide and  after  filtering,  passing  in  excess  of  sulphur  diox- 


52  CHEMISTRY    OF    BERYLLIUM 

ide  and  evaporating  the  solution  in  a  desiccator  in  an  atmosphere 
of  sulphur  dioxide.  No  description  of  the  salt  is  given  other 
than  its  analysis  and  the  fact  that  it  lost  sulphur  dioxide  easily 
when  exposed  to  the  air. 

Ammonium  Beryllium  Sulphite,  2BeSO3.(NH4)2SO3.4H2O.— 
Prepared  by  Rosenheim  and  Woge  ( 1897 ;  4)  in  the  same  man- 
ner as  the  potassium  salt  and  had  similar  properties.  On  ex- 
posure to  air  lost  ammonium  sulphite  as  well  as  sulphur  diox- 
ide. 

Sodium  Beryllium  Sulphite. — Rosenheim  and  Woge  (1897;  4) 
failed  to  prepare  this  salt,  obtaining  only  an  uncrystallizable 
syrup. 

Double  Beryllium  Molybdates. — Rosenheim  and  Woge  (1897; 
4)  were  unable  to  obtain  any  double  salt  with  either  potassium 
sodium  or  ammonium  molybdate. 

DOUBLE  NITRITE. 

Beryllium  Diplatonitrite,  BePt(NO2)4.PtO.9H2O.— Was  pre- 
pared by  Nilson  (1876;  3)  by  treating  barium  platonitrite  with 
barium  sulphate  and  evaporating  in  a  vacuum.  Obtained  small 
bright  red  crystals  which  are  probably  not  a  true  double  salt,  as  in 
solutions  of  these  salts  the  platinum  ion  is  apparently  not  present. 

Beryllium  Platino-di-iodo-nitrite. — Prepared  by  Nilson  (1878; 
7)  in  the  form  of  small,  quadrangular,  yellow  tables  which  de- 
composed at  100°.  Crystals  were  very  deliquescent  and  very 
soluble  in  water. 

DOUBLE  PHOSPHATES. 

Potassium  Beryllium  Orthophosphate,  BeKPO4.  —  Grandeau 
(1886;  2)  first  prepared  this  phosphate  by  fusing  the  sulphate 
of  beryllium  with  acid  potassium  phosphate.  Ouvrard  (1890; 
1 1 )  by  fusing  beryllium  oxide  with  either  meta-,  ortho-  or  pyro- 
phosphate  obtained  the  same  compound  in  rhombic  prisms. 

Sodium  Beryllium  Orthophosphate,  BeNaPO4  and  BeNa4(PO4)2. 
— Wallroth  (1883;  i)  first  obtained  this  phosphate  by  fusing 
beryllium  oxide  in  sodium  metaphosphate.  The  crystals  ob- 
tained were  in  the  form  of  hexagonal  plates.  Ouvrard  (1890; 
1 1 )  obtained  the  same  salt  in  the  same  manner  and  also  by  us- 
ing sodium  pyrophosphate.  He  states  that  his  crystals  were 


DOUBLE  SALTS  OF  BERYLLIUM  53 

identical  with  those  of  beryllonite.  By  using  sodium  ortho- 
phosphate  instead  of  meta-  or  pyrophosphate,  he  obtained  the 
second  phosphate,  Na4Be(PO4)2,  in  lamellae. 

Ammonium  Beryllium  Phosphate. — Rossler  (1878;  9)  has 
shown  that  a  crystalline  precipitate,  similar  to  ammonium  mag- 
nesium phosphate  can  be  produced  by  adding  an  excess  of  am- 
monium phosphate  to  a  beryllium  salt,  adding  hydrochloric  acid 
and  just  neutralizing  with  ammonia,  but  states  that  this  pre- 
cipitate varies  in  composition.  M.  Austin  (1899;  8)  has  also 
worked  with  this  precipitate  in  an  attempt  to  obtain  an  analyt- 
ical method  for  beryllium,  but  agrees  that  the.  results  are  inaccu- 
rate. 

Ammonium  Sodium  Beryllium  Phosphate,  Be(Na)2(NH4)2- 
(PO4)2. — Prepared  according  to  Scheffer  (1859;  3)  by  precip- 
itating beryllium  nitrate  with  sodium  phosphate  in  the  presence 
of  ammonium  chloride. 

DOUBLE  CARBONATES. 

Ammonium  Beryllium  Carbonate. — By  precipitating  an  ammo- 
nium carbonate  solution  of  beryllium  hydroxide  with  alcohol,  a 
white  deposit  is  obtained  which  is  fairly  stable  and  the  compo- 
sition of  which  depends  upon  the  relative  amounts  of  the  con- 
stituents present  and  especially  upon  the  mass  of  the  carbon  di- 
oxide component.  If  such  a  solution  is  boiled  previous  to  the 
addition  of  the  alcohol  and  the  latter  added  at  the  point  where 
the  beryllium  begins  to  separate  as  a  basic  carbonate,  the  precip- 
itate has  the  composition,  3BeCO3.Be(OH)2+3(NH4),CO3,  ac- 
cording to  Debray  (1855;  i)  and  Klatzo  (1869;  i),  while  Hum- 
pidge  (1886;  i)  assigns  to  it  the  formula,  2(BeCO3.(NH4)2CO3>). 
Be(OH)2.2H2O.  This  slowly  loses  ammonia  and  carbon  dioxide 
in  the  cold  and  quickly  on  heating. 

Potassium  Beryllium  Carbonate. — By  a  similar  procedure  to 
the  preceding,  Debray  obtained  a  double  salt  or  a  mixture  to 
which  he  assigned  the  analogous  formula,  3(BeCO3.K2CO3). 
Be(OH)2.  It  was  obtained  in  the  form  of  a  white  precipitate 
by  adding  alcohol  to  a  solution  of  beryllium  hydroxide  in  potas- 
sium carbonate. 


54  CHEMISTRY   OF   BERYLLIUM 

DOUBLE  SILICATES. 

Potassium  Beryllium  Silicate. — Hautefeuille  and  Perrey  (1888; 
5,  1893;  i)  obtained  crystals  of  a  potassium  beryllium  silicate 
of  indefinite  composition  by  fusing  the  constituents  of  a  beryllium 
leucite  in  excess  of  potassium  vanadate.  They  concluded  that 
these  heterogeneous  crystals  were  mixtures  of  simpler  types. 
Friedel  and  Sarasin  (1892;  i)  obtained  a  beryllium  aluminum 
potassium  silicate  in  hexagonal  prisms  by  fusing  the  oxides  of 
the  first  two  in  potassium  silicate.  Duboin  (1896;  5)  obtained 
crystals  of  a  double  silicate  varying  in  composition  between 
2K2O.3BeO.5SiO2  and  2K2O.3BeO.7SiO2  by  dissolving  beryl- 
lium oxide  and  silicon  dioxide  in  potassium  fluoride  and  then 
submitting  to  long  fusion  with  potassium  chloride. 

Sodium  Beryllium  Silicate. — Hautefeuille  and  Perrey  (1890; 
II  and  1893;  i)  in  manner  analogous  to  their  corresponding 
potassium  compounds  by  fusing  the  constituents  of  a  beryllium 
nephelene  in  excess  of  sodium  vanadate,  .obtain  crystals  of  a 
silicate  varying  between  wide  limits  and  which  they  concluded 
were  mixtures  of  simpler  types. 

Lithium  Beryllium  Silicate. — Friedel  (1901;  4)  by  fusing  to- 
gether the  constituents,  obtained  a  silicate  which  he  considered 
a  mixture  of  Li2SiO3  and  Be2SiO4  showing  an  isomorphism 
similar  to  that  between  albite  and  anorthite. 

Aluminum  Beryllium  Silicate,  Be3Al2(SiO3)6. — Artificial  beryl 
has  been  made  by  both  Williams  (1873;  3)  and  by  Hautefeuille 
and  Perrey  (1888;  4)  by  fusing  together  the  proper  mixture  of 
beryllium,  aluminum  and  silicon  oxides,  the  latter  authors  using 
acid  lithium  molybdate  as  a  mineralizing  agent.  The  natural 
color  of  emeralds  may  be  given  by  means  of  chromium,  using  a 
reducing  flame.  Although  Williams  fused  his  beryl  in  the  oxy- 
hydrogen  flame,  the  flame  is  scarcely  hot  enough  to  make  even 
fairly  imitative  emeralds,  the  necessary  mixture  of  gases  to  give 
a  clear  fusion  developing  bubbles  and  oxidizing  the  color. 
DOUBLE  OXALATES. 

Potassium  Beryllium  Oxalate,  BeC,O4.K2C2O4.— Debray  (1855; 
i)  first  obtained  this  oxalate  by  evaporating  the  constituents  to- 
gether, and  his  work  has  since  been  corroborated  by  Rosenheim 


DOUBLE  SALTS  OF  BERYLLIUM  55 

and  Woge  (1897;  4)  and  Wyrouboff  (1902;  i).  Rosenheim 
and  Woge  also  obtained  it  with  one  molecule  of  water  of  crys- 
tallization. Wyrouboff  was  unable  to  measure  the  crystals,  but 
states  that  owing  to  its  comparative  insolubility  it  is  a  promising' 
means  of  separating  beryllium  from  iron  and  aluminum.  In  a 
later  article  (1902;  2)  he  actually  uses  this  property  to  separate 
beryllium  from  beryl,  precipitating  by  means  of  acid  potassium 
oxalate. 

Potassium  Diberyllium  Oxalate,  K2O.2BeO.C2C3+2^H2O. — 
Prepared  by  Philipp  (1883;  2)  by  saturating  acid  potassium 
oxalate  with  beryllium  hydroxide.  Rosenheim  and  Wroge  (1897; 
4)  by  the  same  method  did  not  get  regular  results  as  the  beryl- 
lium hydroxide  dissolved  varied  with  the  condition.  By  saturat- 
ing at  the  boiling  point,  diluting  somewhat  and  allowing  to  stand 
the  excess  of  beryllium  hydroxide  was  deposited  and  on  filtering 
the  solution  and  evaporating  over  sulphuric  acid  distinct  crystals 
separated  out  having  the  above  composition. 

Sodium  Beryllium  Oxalate,  BeC2O4.Na2C2O4.H2O.— Prepared 
by  Rosenheim  and  W7oge  (1897;  4)  and  by  Wyrouboff  (1902; 
i )  in  the  same  manner  as  the  analogous  potassium  compound  and 
resembling  it  closely.  It  gives  off  but  part  of  its  water  at  120° 
and  is  comparatively  insoluble  in  water. 

Sodium  Diberyllium  Oxalate,  Na2O.2BeO.2C2O3+5H2O.— Pre- 
pared by  Rosenheim  and  Woge  (1897;  4)  in  the  same  manner  as 
the  corresponding  potassium  salt.  It  differs  from  it  in  being 
crystallized  only  from  much  more  concentrated  solution. 

Ammonium  Beryllium  Oxalate,  BeC2O4.(NH4)2C2O4. —  Pre- 
pared first  by  Deb  ray  (1855;  i)  by  crystallizing  the  constituents 
together  from  water  solution  and  used  by  him  in  his  determina- 
tions of  the  atomic  weight  of  beryllium.  Philipp  (1883;  2) 
considers  this  salt  characteristic  for  beryllium  and  of  probable 
use  in  separating  the  element.  Rosenheim  and  Woge  (1897; 
4)  also  produced  the  salt.  Its  analysis  is  about  the  only  detail 
given. 

Ammonium  Diberyllium  Oxalate,  (NH4)2O.2BeO.2C2Os. 
2^H2O. — Prepared  by  Rosenheim  and  Woge  (1897;  4)  strict- 
ly analogous  in  composition  and  method  of  preparation  to  the 


56  CHEMISTRY   OF    BERYLLIUM 

corresponding  potassium  salt.  Crystallizable  only  from  a  very 
concentrated  solution. 

Rubidium  Beryllium  Oxalate,  BeC2O4.Rb2C2O4.— Prepared  by 
Wyrouboff  (1902;  i)  in  well  defined  triclinic  crystals  which 
he  measured  and  described.  Axial  ratio  1.0814:1:1.2575,  be— 
78°  40',  ac=86°  46',  ab=io$°  40'.  It  is  more  readily  soluble  in 
water  than  the  potassium  or  sodium  salt. 

Lithium  Beryllium  Oxalate,  BeC2O4.Li2C2O4.2H2O.— Prepared 
by  Wyrouboff  (1902;  i)  in  thin  monoclimc  tables  which  are 
very  soluble  in  water  and  lose  their  water  of  crystallization  at 
110°.  Crystals  were  measured  0.6163:1:1.5445,  ac=gi°  42'. 

DOUBLE  TARTRATES. 

These  salts  have  been  studied  by  Toczynski  (1871;  2),  Ros- 
enheim  and  Woge  (1897;  4)  and  Rosenheim  and  Itzig  (1899; 
13)  and  show  some  remarkable  properties  especially  in  that 
the  beryllium  appears  to  take  the  place  of  the  hydrogen  of  the 
organic  group  as  well  as  the  acid  hydrogen.  The  compounds 
thus  obtained  have  exceptionally  great  molecular  rotation.  Toc- 
zynski reports  two  potassium  beryllium  tartrates,  KBeC4H3O,, 
4- Aq  and  KBe2C4HO6+Aq.  The  first  separated  in  small 
spheres  after  crystallizing  out  some  tartaric  acid  from  a  mixture 
of  two  molecules  of  acid  potassium  tartrate  and  one  molecule  of 
beryllium  hydrate.  The  second  crystallized  in  hemimorphous 
prisms  from  solution  of  acid  potassium  tartrate  saturated  by 
boiling  with  excess  of  beryllium  hydroxide.  It  should  be  iden- 
tical with  the  potassium  diberyllium  tartrate  of  Rosenheim  and 
Woge.  Toczynski  also  obtained  some  glassy  uncrystallizable 
masses  of  antimony  beryllium  tartrate  by  treating  tartaric  acid 
with  antimony  and  beryllium  oxides,  but  they  were  too  indefinite 
to  be  given  place  among  the  compounds  of  beryllium. 

The  double  tartrates  of  beryllium  and  the  alkalies  have  been 
made  the  subject  of  an  extended  research  by  Rosenheim  and 
Woge  (1897;  4)  and  Rosenheim  and  Itzig  (1899;  13)  and  have 
been  carefully  systematized  by  these  authors.  According  to 
them  beryllium  forms  two  series  of  compounds  with  the  alkalies, 
the  monoberyllium  alkali  tartrates  and  the  diberyllium  alkali  tar- 
trates. 


DOUBLE  SALTS  OF  BERYLLIUM  57 

Diberyllium  Alkali  Tartrates,  K2Be4C8H4O13+7H2O,  Na2Be4- 
<J8H4013+ioH20,  ( NH4)  2Be4C8H4013+  ioH2O.— These  salts 
are  obtained  as  beautiful  large  crystals  by  saturating  the  corre- 
sponding bitartrate  with  freshly  precipitated  beryllium  hydrox- 
ide and  evaporating  to  crystallization.  On  recrystallizing  several 
times,  the  salts  were  obtained  pure  and  agreed  empirically  with 
the  above  formulas.  The  authors  believe,  however,  from  the 
molecular  rotation  and  molecular  conductivity  of  these  salts  that 

they  contain  the  complex  anion,  Be4C8H4OI3  and  are  in  reality 
compounds  similar  to  the  copper  and  lead  tartrates  described 
by  Kahlenberg  (Ztschr.  phys.  Chem.,  17,  577),  having  a  double 
molecular  formula  corresponding  to 

COOR  ROOC 

I 

CH(X  /OHC 

>Be    Be/         | 
CHCK  XOHC 

COOBe  — O  —  BeOOC. 

In  their  opinion  the  salts  are  largely  dissociated  even  in  com- 
paratively concentrated  solution,  and  the  complex  anion  is  unusual- 
ly stable  and  subject  but  little  to  hydrolysis  as  the  molecular  ro- 
tation changes  but  little  on  dilution.  They  found  the  molecu- 
lar rotation  of  these  salts  extraordinarily  high.  They  were  cal- 
culated on  the  basis  of  the  water  free  simplest  formulas. 

KBe,C4H307       -  +  225.3 

NaBe2C4H3O7     =  -f  225.1 

NH4Be2C4H307  =  +  241.7. 

Also  the  molecular  conductivity  was  determined 
K(K2Be4C8H40ls  +  7H20),A=/x1024—/A32  =  63.9  — 43-6-20.3, 
^(Na2Be4C8H4013+  ioH2O),  A=^1024— ,x32  =  59.3  —  38.6  =  20.7. 
They  made  no  migration  tests  for  the  presence  of  the  anion. 
Monoberyllium  Alkali  Tartrates,  K2Be2C8H8O13  +  2H2O, 
(NH4)2Be2C8H8O13+2H2O,  Na2Be2C8H8O1,-{-3H2O,  are  rather 
more  indefinite  than  the  diberyllium  salts  as  they  are  not  ob- 
tained as  distinct  crystals.  By  treating  a  slight  excess  of  al- 
kali bitartrate  with  the  calculated  amount  of  beryllium  hydrox- 


5  CHEMISTRY    OF    BERYLLIUM 

ide,  boiling  and  concentration,  the  excess  of  alkali  tartrate  crys- 
tallizes out  and  on  further  evaporation  a  thick  syrup  is  obtained, 
which  on  cooling  solidifies  to  a  mass  of  apparently  constant 
composition.  The  authors  assign  the  double  formula  also  to 
these  residues  corresponding  with  the  type 

COOR  ROOC 

CHOH  HOHC 

I  I 

CHOH  HOHC 

I  I 

COOBe  —  O          BeOOC 

and  believe  it  contains  the  complex  anion,  Be2C8H8OI3.  This 
anion  like  that  of  the  diberyllium  salts  is  very  stable  and  not  hy- 
drolyzed  on  dilution.  The  molecular  rotation  was  determined 
for  the  potassium  and  ammonium  salts  only  as  they  were  not 
able  to  obtain  the  sodium  salt  in  sufficient  quantity  free  from 
excess  of  bitartrate.  The  results  of  many  closely  agreeing  de- 
terminations in  solutions  of  varying  dilution  yielded  for  the 
molecular  rotation,  calculated  on  the  water  free  molecule, 

#   (K2Be.,C8H8013)        =  124-7° 
#((NHJ,BeAH80ls)=  125.8°. 

Ammonium  Diberyllium  Racemate,  (NH4)2Be4C8H4O13+ 
ioH2O;  Ammonium  Monoberyllium  Racemate,  (NH4)2Be2C8H8- 
O13+2H2O. — These  two  salts  were  also  prepared  by  Rosenheim 
and  Itzig  (1899;  13)  and  were  found  to  be  in  every  way  analo- 
gous to  the  corresponding  tartrates  except,  as  was  to  be  expected, 
they  were  optically  inactive.  This  of  course  shows  that  beryl- 
lium has  the  same  effect  of  increasing  the  regular  rotation 
when  substituted  in  the  molecule  of  the  laevo-tartrates  as  has 
been  shown  to  be  the"  case  with  the  dextro-tartrates. 

The  result  of  the  introduction  of  beryllium  into  the  tartrate 
molecule  is  well  shown  by  the  following  table : 
MOLECULAR  ROTATION  [M]^  OF 

Bitartrate         Tartrate      Monoberyllium  Diberyllium 

Tartrate  Tartrate 

Ammonium f  42.8°         +63.0°         4-125.8°  +241.7° 

Potassium 42-5°              64-4°              124.7°  225.3° 

Sodium 41.2°             59-9°  225.1° 


DOUBLE:  SALTS  OF  BERYLLIUM  59 

DOUBLE  MALAXES. 

Rosenheim  and  Itzig  (1899;  13)  by  saturating  laevo-alkali 
acid  malates  with  freshly  precipitated  beryllium  hydroxide  at 
boiling  temperature,  obtained  excellently  crystallized  diberyllium 
malates  in  small  prismatic  crystals.  These  crystals  were  much 
less  soluble  in  water  than  the  corresponding  tartrates  and  con- 
sequently separated  from  comparatively  dilute  solution.  They 
prepared 

Potassium  Diberyllium   Malate,   K2Be4C8H6O12-f  5H2O. 

Sodium  Diberyllium  Malate,  Na2Be4C8H6O12-f  7H2O. 

Ammonium  Diberyllium  Malate,   (NH4)2Be4C8H6O12+4H2O. 

By  precipitating  any  one  of  these  salts  with  dilute  barium 
chloride  solution,  a  precipitate  formed  of  needle-shaped  crystals 
of 

Barium  Diberyllium  Malate,  BaBe4C8H6O12-f  6  or  i2H2O  — 
The  precipitation  of  this  salt  seems  to  lend  additional  evidence 
of  the  existence  of  these  complex  tartrates  and  malates  as 
definite  compounds.  Mercury,  lead  and  silver  salts  threw  down 
only  amorphous  precipitates. 

Rosenheim  and  Itzig  determined  the  molecular  rotation 

^(K2Be4C8H6012)      =  198.9°, 

^(Na2Be4C8H6012)    =  202.2°, 

^(NH4Be4C8H6012)  =  200.9°. 

They  also  determined  the  molecular  conductivity  and  found  for 

^(K2Be4C8H6012),    A  =  ^1024  —  ^  =  63.8  —  45-5  ==  18.3, 
}^(Na2Be4C8H6O12),  A  =  /*1024  —  /x32  —  55.5  —  36.2  =  19.3. 
They  argue  that  these  salts  contain  the  stable  anion,  Be4C8H6O12) 
and  that  the  molecule  is  structurally  according  to  the  type 

COOR  ROOC 

I  I 

CH,  H,C 

I  I 

CHO  —  Be  —  O  —  Be  —  OHC 

COO  —  Be  —  O  —  Be  —  OOC. 

Ammonium  Monoberyllium  Malate,  (NH4)2Be2C8H8O11-f-H2O. 
— This  salt  was  also  prepared  and  studied  by  Rosenheim  and 


60  CHEMISTRY   OF    BERYLLIUM 

Itzig  (1899;  13)  by  the  same  method  as  used  for  the  corre- 
sponding tartrate.  The  sodium  and  potassium  salts  could  not 
be  separated  from  an  excess  of  bimalate.  The  salt  was  obtained 
simply  as  a  non-crystalline  mass  left  on  evaporation.  By  analy- 
sis this  mass  corresponded  to  the  formula  given  above.  The 
molecular  rotation  was  determined  and  found  for  ^(NH4)2 
Be2C8H8On  to  be  106.3°. 

The  strong  influence  which  beryllium  exerts  upon  the  polariza- 
tion of  the  malates  is  shown  by  the  following  table: 

MOLECULAR  ROTATION  [M]#. 

Bimalate  Neutral        Monoberyllium    Diberyllium 

Malate  Malate  Malate 

Ammonium —9.89  -  i3-27          —106.3  -200.9 

Potassium —9.68  -14.26  -198.9 

Sodium —10.02        —  14.31  —202.2 


CHAPTER  VI 


BASIC  COMPOUNDS  OF  BERYLLIUM. 

Some  of  the  most  interesting  problems  of  the  chemistry  of 
beryllium  lie  in  the  equilibrium  relations  between  its  oxide  and 
the  various  acid  radicals.  It  is  certainly  true  that  many  of  these 
acids  can  hold  in  solution  phenominally  large  amounts  of  beryl- 
lium oxide  extending  in  the  case  of  the  acetate  to  six  equiva- 
lents (Ordway,  1858;  i),  while  the  chloride  can  hold  four,  the 
sulphate  three  and  the  oxalate  nearly  three  equivalents.  These 
solutions  on  being  diluted  with  water  throw  down  precipitates 
of  a  highly  basic  nature  or  on  evaporation  leave  gummy  masses, 
the  basicity  of  which  depends  upon  the  concentration  of  the  acid 
used  which  determines  the  amount  of  dissolved  oxide,  or  rather 
hydroxide,  while  they  differ  physically  but  little.  Both  the  pre- 
cipitated bodies  and  the  residues  of  evaporation  are  amor- 
phous and  glassy  in  structure  and  vary  widely  in  compo- 
sition according  to  the  concentration  of  the  solutions  from  which 
they  were  precipitated  and  the  extent  to  which  the  acid  had  dis- 
solved the  base.  The  basic  precipitates  on  washing  with  water  ap- 
proach the  hydroxide  in  composition,  although  the  last  traces  of 
the  acid  radical  are  almost  impossible  to  remove.  These  facts 
have  given  rise  in  literature  to  a  large  number  of  so-called  com- 
pounds of  beryllium  which  in  reality  have  no  existence  as  inde- 
pendent individuals,  but  were  obtained  by  the  analysis  of  the 
indefinite  mixture  or  solid  solution  which  the  particular  con- 
ditions happened  to  yield,  and  in  many  cases,  indeed,  have  no 
further  basis  for  individuality  than  the  per  cent,  of  BeO  they 
were  found  to  contain.  Equilibrium  experiments,  or  repeated 
crystallization  without  change  of  composition,  are  necessary  to 
establish  the  identity  of  individuals,  for  freezing  point  determina- 
tions may  lead  to  erroneous  conclusions  since  the  addition  of 
Be  (OH)  2  to  solutions  of  the  normal  salt  raises  their  freezing 
point  (1907;  10  and  n). 


t>2  CHEMISTRY   OF   BERYLLIUM 

It  is  indeed  difficult  to  understand  how  the  solution  of  the. 
normal  sulphate  and  nitrate  can  dissolve  several  equivalents  of 
their  own  hydroxide,  attack  metals  and  carbonates  almost  as  if 
they  were  sulphuric  or  nitric  acid  themselves,  yielding  these  bas- 
ic substances  and  still  be  less  hydrolyzed  (Leys,  1899;  i,  Brun- 
ner,  1900;  i)  than  the  corresponding  salts  of  iron  and  aluminum- 
Certainly  it  seems  to  be  true  that  all  of  the  so-called  basic 
compounds  of  beryllium,  produced  in  the  presence  of  water  by 
adding  the  hydroxide  or  basic  carbonate  to  a  solution  of  an  acid 
or  a  normal  salt,  have  no  real  existence  as  such,  but  come  only 
in  the  domain  of  homogeneous  phases  of  variable  composition. 
To  this  some  double  salts,  especially  the  tartrates  and  malates 
of  Rosenheim  and  Itzig  (1899;  13),  may  seem  to  be  an  ex- 
ception, for  at  least  some  of  them  are  obtained  crystalline  and 
of  apparent  definite  composition.  It  must  not  be  forgotten,  how- 
ever, that  the  authors  claim  these  to  be  not  basic  in  nature,  but 
complex  and  that  the  excess  of  beryllium  replaces  hydrogen  in 
the  acid  radical,  giving  rise  to  complex  anions  to  which  their 
abnormal  optical  properties  are  due. 

In  contradistinction  to  the  above  substance  we  have,  however, 
the  truly  phenominal  and  actually  basic  compounds  of  beryl- 
lium which  are  produced  pure,  only  in  contact  with  anhydrous 
acid  or  so  nearly  anhydrous  that  the  mass  of  the  water  present 
becomes  negligible  to  produce  hydrolysis.  The  true  basic  com- 
pounds so  far  obtained  belong  solely  to  the  fatty  acid  series.  Their 
solubility  increases  with  the  molecular  weight. 

Basic  Beryllium  Acetate,  Be4O(C2H3O2)0. — This  unique  and 
interesting  chemical  compound  appears  to  be  peculiar  to  beryl- 
lium alone.  It  was  discovered  by  Urbain  and  Lacombe  ( 1901 ; 
2)  who  studied  it  and  described  its  properties.  Parsons  (1904; 
5)  used  it  as  a  means  of  determining  the  atomic  weight  of 
beryllium.  Haber  and  Van  Oordt  (1904;  4)  used  its  solubility 
in  chloroform  as  a  means  of  separating  and  purifying  beryllium 
compounds,  and  Parsons  (1904;  5)  and  Parsons  and  Robertson 
(1906;  i)  used  its  property  of  ready  crystallization  from  hot 
glacial  acetic  acid  for  the  same  purpose. 


BASIC     COMPOUNDS    OF    BERYLLIUM  63 

Basic  beryllium  acetate  melts  at  283° -284°  and  boils  at  330°- 
331°,  and  is  readily  sublimed  without  decomposition.  It  has 
a  vapor  density  agreeing  with  the  formula,  Be4O(C2H3O2)2. 
It  is  itself  almost  insoluble  in  water,  but  is  slowly  hydrolyzed 
by  cold  water  and  quickly  by  hot,  after  which  it  dissolves.  It 
is  easily  soluble  in  absolute  alcohol  and  in  chloro- 
iorm,  and  is  soluble  in  benzene,  toluene,  xylene,  naphtha  and 
all  petroleum  distillates,  turpentine,  methyl  alcohol,  amyl  alco- 
hol, ether,  ethyl  acetate,  acetone  and  carbon  disulphide.  It  is 
also  soluble  in  acetic  anhydride  and  glacial  acetic  acid  and  is  on- 
ly converted  to  the  normal  salt  by  a  mixture  of  these  reagents  on 
heating  to  150°  in  a  closed  tube  (Steinmetz,  1907;  5).  Al- 
though a  basic  compound,  its  solution  in  glacial  acetic  acid  can 
be  saturated  with  hydrochloric  acid  gas  and  remain  unchanged, 
it  is  unaffected  in  dry  air.  Ordinary  acids  attack  it  setting  free 
acetic  acid,  probably  through  the  agency  of  water  they  contain. 
It  is  much  more  soluble  in  boiling  glacial  acetic  acid  than  in 
cold  and  is  most  readily  crystallized  in  this  manner.  On  cool- 
ing, it  separates  from  boiling  glacial  acetic  acid  as  small  shin- 
ing grains  which,  under  a  magnifying  glass,  are  seen  to  be  al- 
most perfect  octahedrons.  The  specific  gravity  of  the  basic  ace- 
tate is  1.362  referred  to  water  at  4°  (Parsons,  1904;  5).  It 
is  best  prepared  by  dissolving  the  carbonate  or  hydroxide  in 
acetic  acid,  evaporating  off  all  water  and  drying  the  residue. 
The  residue  is  then  boiled  in  pure  glacial  acetic  acid  which  dis- 
solves it  completely  and  on  cooling  a  mass  of  small  glistening 
octahedral  crystals  of  the  basic  acetate  are  deposited.  These 
may  be  recrystallized  from  hot  acid  as  many  times  as  desired. 

Vauquelin  (1798;  5)  and  Ordway  (1858;  i)  both  attempted 
to  make  the  acetate  of  beryllium  but  obtained  the  ordinary  gum- 
my form  through  not  being  able  to  understand  the  fact  that 
the  presence  of  water  made  its  preparation  impossible. 

Tanatar  (1904;  3)  also  studied  the  basic  acetate  and  conclud- 
ed that  its  peculiar  properties  led  to  the  supposition  that  beryl- 
lium is  a  tetravalent  element  with  an  atomic  weight  of  18.2. 
His  belief  is  apparently  not  shared  by  others  as  the  valency  of 


64  CHEMISTRY   OF   BERYLLIUM 

beryllium  was  long  ago  established   from  the  vapor  density  of 
the  chloride  and  bromide. 

Basic  Beryllium  Formate,  Be4O(CHO2)6. — This  compound 
was  first  prepared  by  Lacombe  (1902;  3)  by  the  action  of  an- 
hydrous formic  acid  in  excess  on  the  carbonate  and  sublima- 
tion of  the  product  under  diminished  pressure.  Parsons  (1904; 
5)  attempted  to  use  it  for  atomic  weight  determination,  but 
found  its  sublimation  and  purification  too  difficult,  as  even  un- 
der much  diminished  pressure  it  was  partly  decomposed. 

According  to  Lacombe  it  is  insoluble  in  all  solvents  and  as 
it  sublimes  without  fusion,  he  did  not  determine  its  melting  or 
boiling  point.  Tanatar  (1907;  12)  claimed  to  make  it  by  mix- 
ing the  calculated  amounts  of  carbonate  and  acid  and  boiling 
in  water,  which  is  impossible. 

Basic  Beryllium  Propionate,  Be4O(C3H5O2)6. — Was  prepared 
by  Lacombe  (1902;  3)  in  the  same  way  as  the  acetate.  It  is 
a  solid  having  a  melting  point  of  H9°-I2O°  and  a  boiling 
point  of  339°-34i°.  It  sublimes  at  221°  under  19  millimeters 
pressure.  No  other  details  given.  Tanatar  (1907;  12)  by 
treating  with  acetyl  chloride  obtained  crystals  of  Be4O(C3H5- 
O2)3(C2H,O2)3  with  melting  point  127°  and  boiling  point  330°. 
Boiling  without  decomposition.  Soluble  in  ether  and  benzene. 

Basic  Beryllium  Isobutyrate,  Be4O(C4H7O2)6. — 'Prepared  by 
Lacombe  (1902;  3)  in  manner  analogous  to  the  acetate,  is  a 
solid  melting  at  76°  and  boiling  at  336°-337°.  Under  19  mil- 
limeters pressure  :t  sublimes  at  216°.  No  other  details  given. 

Basic  Beryllium  Butyrate,  Be4O(C4H7O2)6. — Is  a  liquid  pre- 
pared in  the  same  way  as  the  acetate  by  Lacombe  (1902;  3) 
which  boils  at  239°  under  19  millimeters  pressure.  No  other 
oetails  given.  Tanatar  (1907;  12),  by  treating  this  with  acetyl 
chloride,  obtained  Be4O(C4H7O2)4.(C2H3O2)2  a  liquid  soluble 
in  benzene  and  ether,  melting  at  — 15°  and  boiling  at  351°. 

Basic  Beryllium  Isovalerianate,  Be4O(C5t!9O2)6. — Is  a  liquid 
prepared  by  Lacombe  (1902;  3)  in  the  same  way  as  the  acetate. 
Jt  boils  at  254°  under  19  millimeters  pressure.  No  other  de- 
tails given. 


BASIC     COMPOUNDS    OF    BERYUJUM  65 

INDEFINITE  BASIC  BERYLLIUM  SOLID  PHASES. 

Among  the  basic  beryllium  substances  which  are  of  variable 
composition,  but  to  which  formulas  have  been  assigned,  the 
sulphates,  oxalates  and  carbonates  have  been  most  studied  and 
in  the  first  two  cases  they  have  been  shown  to  be  simply  solid 
solutions  of  the  hydroxide  and  the  normal  salt.  These  three 
only  are  worthy  of  separate  mention. 

BASIC  SULPHATES. 

Berzelius  (1815;  i)  first  showed  that  beryllium  sulphate  dis- 
solves its  own  hydroxide  in  quantity  although  Vauquelin  (1898; 
5)  and  Gmeiin  (1801;  i)  had  already  produced  a  gummy  sul- 
phate. Berzelius  assigned  the  formulas,  3BeO.SO3  and  2BeO. 
SO3,  to  the  evaporated  residue  of  the  corresponding  solution 
for  no  other  apparent  reason  than  that  they  represented  whole 
equivalents,  although  he  must  have  known  that  any  interme- 
diate ratio  between  3BeO.SO3  and  BeO.SO3  was  as  easily  ob- 
tained and  that  any  one  of  these  residues  had  as  good  claim  to 
the  dignity  of  being  a  compound.  To  the  basic  precipitate  ob- 
tained by  diluting  the  concentrated  solution  of  3BeO.SO3  with 
water,  Berzelius  gave  the  formula,  6BeO.SO3.3H2O.  Debray 
(1855;  i),  many  years  later,  used  these  basic  sulphates  as  a 
method  of  separation  from  aluminum  but  assigned  no  formulas. 
Atterberg  (1873;  7)  also  obtained  precipitates  by  diluting  with 
water  the  strong  solution  of  BeSO4  saturated  with  Be(OH)2 
and  assigned  formulas,  BeSO4.5Be(OH)2-f 2H2O  and  BeSO4. 
7Be(OH)2-(-H2O.  He  also  again  'evaporated  solutions  con- 
taining three  and  two  equivalents  of  the  oxide  to  one  of  acid 
and  of  course  obtained  residues  of  that  ratio  corresponding  to 
the  first  two  formulas  assigned  by  Berzelius.  Parsons  (1904; 
10)  attacked  this  problem  by  means  of  equilibrium  experiments 
in  a  large  specially  constructed  thermostat  and  showed  that  the 
precipitates  obtained  by  diluting  the  more  basic  solutions  con- 
sisted of  a  single  phase,  that  they  had  a  ratio  when  equilibrium 
was  reached  as  high  as  25BeO  to  iSO3,  that  they  varied  in  com- 
position and  that,  therefore,  they  could  only  be  a  solid  solution 
of  the  hydroxide  containing  a  small  amount  of  the  normal  salt. 
He  also  studied  the  basic  liquid  solution  and  showed  that  there 
5 


66  CHEMISTRY   OF   BERYLLIUM 

was   nothing   characteristic   in   the  residue  obtained  by   evapo- 
rating any  particular  ratio  of  acid  to  base. 

Parsons  and  Robinson  and  Fuller  (1906;  3,  1907;  10)  again 
took  up  the  question  of  the  solution  of  Be(OH)2  in  BeSO4 
solution  and  showed  that  the  freezing  point  was  raised  and  the 
conductivity  lowered  thereby,  and  that  no  anion  containing 
beryllium  was  formed.  They  also  showed  that  on  dialyzing 
such  solutions  into  water,  beryllium  hydroxide  invariably  sep- 
arated out  and  the  solution  left  behind  always  had  a  higher 
basic  ratio  than  that  which  had  passed  through  the  parchment. 

All  these  facts  prove  that  none  of  these  substances  are  true 
compounds,  but  merely  solutions  of  some  form  or  other.  It 
seems  quite  probable  that  beryllium  sulphate  once  dissolved  acts 
simply  as  a  liquid  in  which  its  own  hydroxide  is  soluble  (1907; 
ii). 

BASIC  OXALATES. 

These  substances  hold  a  strictly  analogous  position  to  the 
sulphates  already  mentioned.  Vauquelin  (1798;  5)  and  Debray 
(1855;  i)  had  obtained  simply  gummy  basic  masses  and  appar- 
ently realizing  that  they  were  not  true  compounds  gave  them 
no  formulas.  Atterberg  (1873;  7)  had  the  same  experience, 
but  assigned  the  formula,  BeC2O4.Be(OH)2.H2O,  to  the  mass 
obtained  by  evaporating  the  solution  of  one  equivalent  of  the 
hydroxide  in  one  equivalent  of  the  normal  oxalate  and  the  for- 
mula, BeC2O4.6Be(OH)2.6H2O,  to  the  highly  basic  precipitate 
obtained  by  diluting  the  solution  of  the  first  with  a  large  ex- 
cess of  water.  Parsons  and  Robinson  (1906;  i)  studied  these 
basic  oxalates  by  phase  rule  considerations,  by  the  same  method 
as  had  been  used  on  the  basic  sulphates  and  showed  that  when 
equilibrium  was  reached  the  precipitated  basic  oxalates  had  a 
ratio  as  high  as  25BeO  to  iC2O4,  that  they  varied  in  composi- 
tion, that  they  consisted  of  a  single  phase  and  must,  therefore, 
be  simply  a  solid  solution  of  the  oxalate  in  the  hydroxide  or  the 
simple  hydroxide  occluding  some  of  the  normal  salt.  The  basic 
solutions  like  the  sulphate  appear  to  be  a  case  of  simple  solution 
of  the  hydroxide  in  a  mixed  solvent  consisting  of  water  and 
beryllium  oxalate.  When  the  concentration  of  beryllium  ox- 


BASIC     COMPOUNDS    OF    BERYLUUM  67 

alate  in  such  a  solution  reaches  its  maximum,  it  will  dissolve 
1.85  equivalents  of  beryllium  hydroxide. 

BASIC  CARBONATE. 

When  salts  of  beryllium  are  precipitated  with  sodium  or  potas- 
sium carbonates  or  when  an  ammonium  carbonate  or  sodium  bi- 
carbonate solution  of  beryllium  hydroxide  is  boiled,  a  highly  basic 
precipitate  is  thrown  down  to  which  the  following  formulas  have 
been  assigned. 

2BeCO.,7Be(OH)2.2H2O,  ( Schaffgotsch,  1840;  2).  2Be- 
C08.7Be(OH)2.3H2O  and  4BeCO3.8Be(OH)2.5H2O  (Weer- 
en,  1854;  i).  BeC03.2Be(OH)2.3H20,  (Debray,  1855;  i), 
(Klatzo,  1869;  i).  BeC03.2Be(OH)2.Aq  (Parkman,  1862;  i). 
BeC03.5Be(OH)2.3H2O,  (Seubert  and  Elten  1893;  4).  BeCO3. 
2Be(OH)2.2H2O,  (Pollok,  1904;  i). 

These  formulas  represent  little  else  than  an  approximation  at 
equilibrium  between  BeO,  CO2  and  H2O  under  the  conditions 
present.  In  the  presence  of  the  largest  possible  amount  of  the 
carbon  dioxide  the  composition  is  approximately  represented  by 
one  equivalent  of  the  carbonate  to  two  of  the  hydroxide,  but 
boiling  which  not  only  increases  hydrolysis,  but  removes  car- 
bon dioxide  from  the  system,  slowly  causes  the  solid  phase  to 
approach  the  pure  hydroxide.  There  is  nothing  in  literature 
to  indicate  that  anyone  of  the  intermediate  stages  represents  a 
true  compound  and  this  is  apparently  realized  by  one  or  two  of 
the  authors. 

Chemically  the  basic  precipitate  is  much  the  same  whether  it 
is  thrown  down  by  a  soluble  carbonate  or  by  boiling  an  ammo- 
nium carbonate  or  diluted  acid  sodium  carbonate  solution.  In 
either  case  it  occludes  notable  quantities  of  the  precipitant, 
which  can  not  be  removed  by  washing  and  the  author  has  never 
found  less  thati  two  per  cent,  so  contained.  This  fact  is  not 
generally  realized,  but  is  of  decided  importance  when  this  sub- 
stance is  to  be  used  as  a  basis  for  the  preparation  of  other 
compounds.  In  the  case  of  occluded  ammonia  it  can  be  re- 
moved by  prolonged  boiling  or  by  intermittently  passing  car- 
bon dioxide  through  the  precipitate  suspended  in  water,  filter- 
ing off  the  liquid  and  repeating.  Many  hours  boiling  is  required 
by  the  first  procedure  and  the  residue  left  is  almost  the  pure 


68  CHEMISTRY  OF   BERYLLIUM 

hydroxide,  while  if  the  second  method  is  used  the  purification  is 
a  matter  of  days,  but  the  residue  is  about  as  rich  in  the  CO2  com- 
ponent as  when  first  precipitated.  Passing  carbon  dioxide  through 
the  boiling  liquid  has  little  effect  on  the  result  as  would  natural- 
ly be  expected.  The  ammonia  may  be  removed  with  but  little 
loss  of  carbon  dioxide,  by  momentarily  boiling  with  steam,  filter- 
ing, addition  of  fresh  cold  water  and  repeating  several  times. 
Ordinary  washing  with  hot  water  does  not  seem  to  be  effective. 
Drying  at  100°  does  not  remove  the  occluded  ammonia,  but  its 
odor  becomes  immediately  apparent  on  heating  to  the  point 
where  the  carbon  dioxide  begins  to  be  evolved. 

Physically  the  precipitates  thrown  down  by  alkaline  carbon- 
ates are  quite  different  from  the  precipitate  on  boiling  an  am- 
monium carbonate  solution;  the  first  being  gelatinous  and  dif- 
ficult to  wash  while  the  latter  comes  down  in  granular  condi- 
tion and  filters  most  readily.  A  saturated  solution  of  ammo- 
nium carbonate  will  dissolve  an  amount  of  freshly  precipitated 
beryllium  carbonate  or  hydroxide  equivalent  to  22  grams  BeO 
in  1000  cubic  centimeters  (Pollok,  1904;  i).  On  boiling  this 
solution,  carbon  dioxide  and  ammonia  escape  rapidly  and  soon 
the  basic  carbonate  precipitate  begins  to  appear  in  fine  white 
granular  form.  The  boiling  is  best  done  by  means  of  steam  as 
otherwise  very  violent  bumping  takes  place  which  continuous 
stirring  will  not  entirely  prevent.  The  first  portions  of  the 
precipitate  thrown  down  by  boiling  a  solution  saturated  with 
ammonium  carbonate  are  rather  richer  in  carbon  dioxide  than 
those  that  follow  having  a  composition  approximating  BeCOs.- 
BeCO3.sBe(OH)2.3H2O,  (Seubert  and  Elten  1893;  4).  BeCO3 
the  boiling  is  continued  in  such  a  solution  until  precipitation  is 
complete  the  composition  is  approximately  BeCO3.+2H2O 
(Parsons,  1904;  5).  If,  on  the  other  hand,  the  solu- 
tion is  diluted,  some  four  or  five  times  hydrolysis  of  the  whole 
material  present  takes  place  with  very  little  boiling,  and  the 
granular  carbonate  thrown  down  appears  to  have  the  approx- 
imate composition  BeCO3.2Be(OH)2+Aq.  This  material  can 
be  dried  at  150°  without  notable  loss  of  carbon  dioxide.  Fur- 
ther boiling  causes  gradual  loss  of  carbon  dioxide  and  eventual- 


BASIC   COMPOUNDS   OF   BERYUJUM  69 

ly  only  the  hydroxide  is  left.  Attempts  by  the  writer  to  in- 
crease the  carbon  dioxide  component  in  the  precipitate,  be- 
yond that  already  indicated  by  passing  the  gas  under  pressure 
over  the  precipitate  and  also  over  freshly  precipitated  hydroxide 
have  so  far  proven  unavailing. 

The  basic  carbonate  obtained  by  boiling  the  ammonium  car- 
bonate solution,  while  of  no  definite  composition,  is  quite  pro- 
perly a  favorite  material  to  be  used  as  a  basis  for  the  production 
of  beryllium  salts  since  it  dissolves  readily  in  acids  and  if  care 
is  taken  to  remove  all  the  occluded  ammonia  a  pure  salt  is  ob- 
tained at  once.  Acid  sodium  carbonate  is  an  equally  good  sol- 
vent and  on  diluting  a  saturated  solution  some  four  or  five 
times  and  boiling  the  basic  carbonate  is  thrown  down,  but  is 
more  difficult  to  obtain  in  granular  form.  The  occluded  so- 
dium carbonate  moreover  can  not,  of  course,  be  volatilized  off. 

MISCELLANEOUS   BASIC  SOLID  PHASES. 

Besides  the  basic  sulphates,  oxalates  and  carbonates,  already 
enumerated,  many  other  gummy  precipitates  and  residues  of 
evaporation  have  been  assigned  formulas  as  definite  compounds 
and  find  place  in  the  literature  of  beryllium.  They  are  all 
prepared  in  much  the  same  way  and  generally  by  saturating  the 
solution  of  an  acid  or  of  a  normal  salt  with  beryllium  hydroxide 
or  carbonate  and  by  evaporation  or  diluting  with  water  obtaining 
a  solid  phase  which  is  generally  more  or  less  changed  by  fur- 
ther washing  with  water.  In  the  opinion  of  the  writer  none  of 
these  "so-called"  compounds,  appearing  in  literature,  of  which  the 
following  is  a  list,  have  any  proven  claim  for  individual  existence, 
but  are  in  reality  solid  solutions  of  the  normal  salt  with  the  hy- 
droxide or,  what  is  much  the  same  thing,  the  hydroxide  with 
more  or  less  occluded  normal  salt. 
Basic  sulphites: 

2BeSO3.9Be(OH)2.6H2O,  Seubert  and  Elten,  1893;  4. 

BeS03.Be(OH)2.2H20,  Atterberg,  1873;  7. 

BeSO3.Be(OH)2.Aq,  Kriiss  and  Moraht,   1890;  4. 

3BeS04.Be(OH)2.Aq 
Basic  Dithionate: 

2BeS2O6.3Be(OH)2+i4H2O,  Kluss,   1888;  2. 


7O  CHEMISTRY   OF    BERYLLIUM 

Basic  chlorides: 

3BeCl2.2Be(OH)2,  Atterberg,  1873;  7. 

BeCl,.3Be(OH)2,  Atterberg,   1873;  7. 

BeCl2.i2Be(OH)2+ioH8O,  Atterberg,   1873;  7. 

BeCl2.i2Be(OH)24-4H2O,    Atterberg,    1873;    7. 

Be(OH)Cl,  Atterberg,  1875;  4. 
Basic  selenites: 

2BeSeO3.Be(OH)2+2H2O,  Atterberg,   1873;  7. 

BeSe03.Be(OH)2.H2O,  Atterberg,    1873;   7. 

2BeSeO3.3Be(OH)2.7H2O,  Nilson,   1875;  2. 
Basic  borates: 

Be(BO3)2.2Be(OH)2+Aq,  Kriiss  and  Moraht,  1890;  4. 
Basic  nitrate: 

Be(N03)2.Be(OH)2.2H2O,  Ordway,    1858;    i. 
Basic  chr ornate : 

BeCrO4.i3Be(OH)2+ioH2O,   Atterberg,    1873;   7. 

BeCrO4.6Be(OH)2,  Glassmann,   1907;  4. 
Basic  molybdate: 

BeMo04.Be(OH)2.2H2O,  Atterberg,  1873;  7. 
Basic  succinate : 

BeC4H4O4.Be(OH)2-U2H2O,   Atterberg,   1873;   7. 
basic  ferro cyanide : 

Be2FeCy6.4Be(OH)2+7H2O,  Atterberg,   1873;   7. 
Also  basic  salts  of  the  formula  Be4O(Ac)6  or  Be2O(Ac)2  claimed 
to  be  obtained  by  adding  the  carbonate  to  aqueous  solution  of 
the  acid  and  evaporating. 
Basic  crotonate: 

Be4O(C4H6O2)6,  Tanatar    (1907;   12). 
Basic  isocrotonate : 

Be40(C4H502)6;  Tanatar  (1907;  12). 
Basic  laevulinate : 

Be4O(C5H7O8)6,    Tanatar    (1907;    12). 
Basic  succinate : 

Be4O(C4H4O4)3,   Tanatar    (1907;    12). 
Basic  cyanacetate: 

Be4O(C2H2CNO2)6,  Glassmann,    (1908;   i). 
Basic  dichloracetate : 


BASIC   COMPOUNDS  OF   BERYLLIUM  71 

Be4O(C2HCl2O2)6,  Glassmann,   (1908;  i). 
Basic  monochloracetate: 

Be4O(C2H2ClO2)6,  Glassmann,   (1908;  i). 
Basic  monobromacetate : 

Be4O(C2H2BrO2)6,    Glassmann,    (1908;    i). 
Basic  monobrompropionate : 

Be4O(C3H4BrO2)6,  Glassmann,   (1908;   i). 
Basic  lactate: 

Be2O(C3H5O3)2.H2O,  Glassmann,  (1908;!). 
Basic  glycolate : 

Be2O(C2H3O3)2.H2O,  Glassmann,  1908;  i). 
Basic  trichloracetate : 

Be2O(C2Cl3O2)2,  Glassmann,   (1908;   i). 
Basic  ethyl  glycolate : 

Be2O(C2H5C2H2O3)2.H,O,  Glassmann,  (1908;  i). 
Basic  phenyl glycolate : 

Be2O(C6H5C2H2O3)2,  Glassmann,   (1908;   i). 
Basic  chloropropionate : 

Be2O(C3H4ClO2)2.H2O,  GUassman,  (1908;  i). 
Basic  salicylate: 

Be2O(C7H5O3)2,  Glassmann,   (1908;   i). 

Basic  beryllium  chlorides  (Vauquelin,  1798;  5,  Gmelin, 
1801 ;  i),  Nitrates  (Vauquelin,  1798;  6,  Gmelin,  1801 ;  i). 
Hypophosphites  (Rose,  1828;  i),  V derates  (Trommsdorff, 
J833;  i),  Oxalates,  citrates,  tartrates  and  acetates  (Vauquelin 
T798;  5)  to  which  no  formulas  were  assigned  nor  analyses 
made. 


PART  II. 


BIBLIOGRAPHY  OF  BERYLLIUM. 

1798;  i.  Vauquelin,  L.  N.  De  1'Aigue  marine,  ou  Beril;  et 
decouverte  d'une  terre  nouvelle  dans  cette  pierre. 
Read  at  the  Institute  26  Pluviose,  An  6  (Feb.  14, 
1898).  Announces  the  discovery  of  a  new  earth,  "la 
terre  du  Beril,"  separated  from  aluminum  by  the  pre- 
cipitation of  Be  (OH)  2  from  KOH  solution  on  boiling. 
Differs  from  aluminum  in  its  salts  being  sweet,  having 
a  greater  affinity  for  acids,  giving  no  alum,  soluble  in 
(NH4)2CO3,  soluble  and  not  being  precipitated  by 
K2C2O4  or  K2C4H4O6.  Editors  suggest  name  "glucine" 
in  foot  note. 

Ann.  de  chim.,  26  (1798)  155-170; 

Allg.  J.  Chem.,  i,  (1798)  341; 
.  Nicholson's  J.,  2,  358; 

Chem.  Ann.  (Crell),  14,  422. 
1798;  2.     Vauquelin,  L.  N.     Sur  la  terre  du  Beril;  pour  ser- 

vir  au  premier  memoire  sur  le  meme  object. 
Studies  new  earth  and  gives  following  specific  char- 
acters, sweet  and  astringent  salts,  very  soluble  in  H2- 
SO4,  decomposes  salts  of  aluminum,  soluble  in  NH4OH, 
affinity  for  acids  between  magnesium  and  aluminum, 
soluble  in  fixed  alkalies,  infusible,  soluble  in  acids  ex- 
cept carbonic  and  phosphoric,  fusible  with  borax,  ab- 
sorbs one-fourth  of  its  weight  of  CO2,  not  precipitated 
by  saturated  hydrosulphides. 

Ann.  de  chim.,  26,  170-177; 

Nicholson's  J.,  2,  393 ; 

Chem.  Ann.  (Crell),  14,  434. 

3-  Vauquelin,  L.  N.  Same  as  1798;  i.  Again  read 
before  the  French  Society  of  Mines,  and  Vauquelin, 
in  a  foot  note,  refers  to  the  proposed  name  glucine, 
but  does  not  adopt  it  in  text. 

J.  des  mines,  8,  553"564- 


BIBLIOGRAPHY    OF    BERYLLIUM  73 

1798;  4.  Vauquelin,  L.  N.  Analyse  de  1'emeraude  du  Peron. 
Shows  identity  of  beryl  and  emerald  and  uses  word 
glucine  for  first  time,  saying  "on  a  donne  le  nom  de 
giucine." 

Ann.  de  chim.,  26,  259. 

Allg.  J.  Chem.  (Scherer),  I,  361. 

X798;  5-  Vauquelin,  L.  N.  Ueber  die  Verhaltnisse  der  Glu- 
cine zu  den  Saueren. 

Made  sulphate,  nitrate,  chloride,  phosphate,  carbon- 
ate, citrate,  tartrate,  acetate,  mostly  in  gummy  basic 
masses.  Purified  from  iron  by  means  of  KHS. 

Allg.  J.   Chem.    (Scherer),   I,   590-596. 

1799;  i.  Vauquelin,  L.  N.  Sur  Tanalyse  des  pierres  en  gen- 
eral et  resultats  de  plusieurs  de  ces  analyses  faites  au 
laboratoire  de  1'ecole  des  mines  depuis  quelques  mois. 
Points  out  how  to  recognize  beryllium  in  rocks. 

Ann.  de  chim.,  30,  82. 

1799;  2.  Vauquelin,  L.  N.  Anleitung  zur  Zerlegung  der 
Fossilien. 

Allg.  J.  Chem.  (Scherer),  3,  430. 

1799;  3.  Link,  H.  F.  "Correspondence."  Objects  to  name 
glucine  because  it  resembles  glycine,  already  in  use. 

Allg.  J.  Chem.  (Scherer),  3,  603. 

1800;  i.  Klaproth,  M.  H.  In  the  third  volume,  page  78  of  his 
Beitrage  Zur  Kentniss  der  Mineralkorper,  he  refers 
to  a  paper  read  by  himself  before  the  royal  Academy 
of  Sciences  of  Berlin  on  Sept.  11,  1800,  in  which  he 
argues  against  the  name  "Glycine,"  proposed  for  Vau- 
quelin'"s  earth,  on  the  ground  that  sweetness  is  not 
unique  to  that  element,  but  is  also  possessed  by  the 
yttrium  earth  and  further  is  too  much  like  "Glycine" 
which  Link  had  already  pointed  out.  Claims  "Beryl- 
lerde''  should  be  used. 

1801;  i.  Gmelin,  H.  R.  Zerlegung  des  Berylls  von  Nert- 
schink  in  Sibirien  und  Priifung  der  daraus  erhalten 
Susserde. 


74  CHEMISTRY   OF   BERYLLIUM 

Confirms     Vauquelin's     discovery.        Short     unimpor- 
tant study  of  nitrate,  chloride  and  sulphate. 

Chem.  Ann.    (Crell),   17,  89. 

1 80 1 ;  2.  Schaub,  T.  Chemische  Untersuchung  des  blauen 
siberischen  Berills. 

Fuses    beryl    with    NaOH    and    KOH    in    silver   cru- 
cible.    Confirms  Vauquelin's  discovery. 

Chem.  Ann.   (Crell),   17,  174. 

1802;  i.  Ekeberg,  A.  G.  Sur  quelques  proprietes  de  1'yttria 
compares  avec  celles  de  la  glucine. 
Beryllium  is  precipitated  from  solution  by  the  succin- 
ates,  colorless  salts,  soluble  in  KOH,  and  not  precip- 
itated by  alkaline  prussates.  Chief  differences  from 
yttria.  Specific  gravity  660=2.967. 

J.  des  mines,  12,  245. 

1809;  i.  Davy,  Humphrey.  On  some  new  electro-chemical 
researches  on  various  Objects,  particularly  the  metal- 
lic bodies  from  the  alkalies,  an  earths,  and  on  some 
Combinations  of  Hydrogen. 

Attempted  to  reduce  BeO  in  platinum  tube  by  potas- 
sium   vapor    without    certain    result.        On    fusing    BeO 
in   clay   crucible   with   iron   filings   and   potassium   ob- 
tained a  semi-malleable  mass. 

Phil.  Trans.,  London,  100,  59. 

Ann.  der  Phys.   (Gilbert),  32,  395. 

Ann.  d.  chim.,   (i)  75,  150. 

Phil.  Mag.,  32,  152,  203. 

1811;  i.  Gay-Lussac,  L.  J.,  and  Thenard,  L.  J.  Recherches 
Physico-ch'imique. 

Made  a  fluoride  of  beryllium  by  precipitating  HKF2 
with  beryllium  oxide  dissolved  in  hydrochloric  acid. 
Ann.  d.  chim.,    (i)   78,  275. 

181 1  ;  2.     John,  J.  F.     Ueber  einige  unbekannte  Verbindung;en 
der  Chromsauere  mit  verschiedenen   Basen. 
Dissolved  basic  carbonate   in   chromic  acid,  but   could 
not  crystallize  any   salt. 


BIBLIOGRAPHY    OF    BERYLLIUM  75 

1812;  i.  Stromeyer,  F.  Du  memoire  stir  la  reduction  de  la 
terre  silicee,  operee  par  le  moyen  du  charbon  et  du 
fer. 

Claimed  that  he  reduced  magnesium  and  beryllium 
with  great  success  by  mixing  the  oxides  with  carbon, 
iron  and  linseed  oil  to  a  paste  and  melting  in  closed 
crucible,  obtaining  alloys  with  iron.  Stromeyer  was 
mistaken. 

Ann.  d.  chim.,   (i)  81,  257. 

1815;  i.  Berzelius,  J.  J.  Versuch  durch  Anwendung  der  Elek- 
trochemische  (Theorie  und  der  chemischen  Propor1- 
tion  Lehre  Analyse  der  Beryllerde. 
Prepared  crystals  for  the  first  time  of  BeSO44H2O, 
which  he  considered  an  acid  salt.  By  dissolving  one 
and  two  equivalents  of  beryllium  carbonate  in  this 
salt,  he  obtained  on  evaporation  gummy  masses  con- 
taining the  ratios  2BeO.SO3  and  3BeO.SO3  respec- 
tively. The  first  of  these  he  considered  the  normal 
sulphate  and  the  second  a  basic  salt.  On  diluting 
the  last  with  water  he  obtained  a  white  precipitate  to 
which  he  assigned  the  ratio  6BeO.SO3.  He  also  de- 
termined the  atomic  weight  of  beryllium  from  BeSO4. 
4H2O  and  analyzed  an  impure  chloride. 
J.  .fur  Chem.  (Schweigger),  15,  296. 

1823;    i.     Berzelius,   J.   J.       Untersuchungen   iiber   die   Fluss- 
spathesaure  und  deren  merkwurdigsten  Verbindungen. 

Vet.  Akad.  Handl.   (Stockholm),  1823,  302. 

Ann.  der  Phys.  (Pogg),  i,  22,  196. 

Annals  of  Phil.  (Thomson),  24,  330. 
Made  and  described  BeF2.  Dissolved  BeO  in  HF. 
Obtained  an  easily  soluble  substance  which  dries  to  a 
gummy  mass  and  which  loses  H2O  at  100°,  becoming 
milk  white  and  foamy.  Loses  part  of  its  HF  on  ig- 
nition. Yields  double  salts  with  alkalies  of  which  the 
potassium  salt  is  very  insoluble.  Obtained  a  beryl- 
lium fluosilicate  by  action  of  fluosilicic  acid. 


76  CHEMISTRY   OF   BERYLLIUM 

1823;  2.  Du  Menil.  Analyse  des  Sibirischen  hellblaulichen 
Berylls  (  Aquamarine ) . 

J.  fur  Chem.    (Schweigger),  39,  487. 
Details  method  of  analysis. 

1825 ;    i.     Berzelius,  J.  J.     Ueber  die  Schwefelsalze. 

Kongl.  Vet.  Acad.  Hand!.,  1825,  253;  275,  288,  311. 
Ann.  d.  Phys.  (Pogg),  6,  453;  7,  23,  144,  273. 
Was  not  able  to  produce  a  sulphide  of  Be  in  solution. 

1826;  I.  Berzelius,  J.  J.  Ueber  die  Bestimmung  der  relativen 
Anzahl  von  emfachen  Atomen  in  chemischen  Verbind- 
ungen. 

Ann.  d.  Phys.   (Pogg),  8,  187. 

Valueless  data  on  atomic  weight,  as  he  used  a  very 
basic  sulphate.  Gives  oxides  as  Be,O3. 

1826;  2.     Berzelius,  J.  J.     Ueber  die  Schwefelsalze. 

Kongl.  Vet.  Acad.  Handl,  1826,  part  I,  53. 

Ann.   d.    Phys.    (Pogg),   8,   279. 

Thought  he  made  a  double  sulphide  of  tungsten  and 
beryllium  by  precipitating  the  double  sulphide  of  po- 
tassium and  tungsten  with  a  beryllium  salt.  No  for- 
mula or  details. 

1827;  I.  Rose,  H.  Ueber  die  Verbindungen  des  Phosphors 
mit  den  Wasserstoffe  und  den  Metallen. 

Ann.  d.  Phys.   (Pogg),  9,  39. 

Berzelius  Jsb.,  8,  174. 

Ann.  des  Mines,  (2)  3,  146. 

Made  BeCl2  anhydrous  for  the  first  time.  Passed 
chlorine  over  a  heated  mixture  of  the  oxide  and  carbon 
and  sublimed  the  product.  Made  beryllium  phosphite 
by  precipitating  BeCl2  with  a  saturated  solution  of 
PC18  in  NH4OH. 

1828;  i.     Rose,  H.     Ueber  die  unter  Phosphorichtsauren  Salze. 

Ann.  der  Phys.   (Pogg),  12,  86. 

By  saturating  the  acid  with  beryllium  hydroxide  ob- 
tained only  a  non-crystallizable  gummy  mass. 


BIBLIOGRAPHY    OF    BERYLLIUM  77 

1828;  2.     Wohler,  F.     Ueber  das  Beryllium  und  Yttrium. 

Ann.  d.  Phys.   (Pogg),  13,  577- 

Berzelius  Jsb.,  9,  96. 

Mag.  fur  Pharm.,  26,  257. 

Ann.  des  Mines,   (2)  5,  133. 

Ann.  chim.  phys.,  (2)  39,  77. 

Reduced  sublimed  BeCl2  with  potassium  in  platinum 
crucible  and  for  the  first  time  obtained  metallic  beryl- 
lium as  a  dark  grey  powder.  Gives  following  proper- 
ties, not  all  of  which  are  sustained  by  later  investiga- 
tors :  Burns  in  air  and  oxygen  to  BeO  when  heated  on 
platinum.  Dissolves  in  concentrated  H2SO4,  yielding 
SO2.  Dissolves  in  dilute  H2SO4,  HC1  and  KOH,  giv- 
ing off  hydrogen.  Dissolves  in  dilute  HNO3  giving 
off  nitric  oxide.  Not  affected  by  NH4OH.  Burns  in 
chlorine  and  bromine  to  BeCl2  and  BeBr2,  both  easily 
volatile  and  soluble  with  evolution  of  much  heat.  Burns 
in  iodine  gas  and  sublimes  as  BeI2  with  properties  sim- 
ilar to  BeCl2  and  BeBr2.  BeS,  made  by  heating  in  sul- 
phur vapor  is  a  grey  infusible  mass  difficultly  soluble 
in  H2O  which  yields  H2S  with  acids. 
BeSe,  made  by  heating  in  melted  Se  is  fusible,  but 
difficultly  soluble.  BeTe,  a  grey  powder.  Made  beryl- 
lium phosphide  by  heating  with  phosphorous  and  beryl- 
lium arsenide  by  fusing  with  arsenic. 

1828;   3.     Bussy.     Preparation   du  glucinium.     Read  at  Acad. 
Roy.  de  Medic,  Aug.  16,  1828. 

J.  chim.  medicale,  4,  453. 

J.  fur  Chem.   (Schweigger),  54,  241. 

Berzelius  Jsb.,  9,  97. 

J.  de  pharm.,  1828,  486. 

Polyt.  J.  (Dingier),  29,  466. 

Prepared  beryllium  almost  simultaneously  with  Woh- 
ler and  by  the  same  method.  Obtained  an  impure  pro- 
duct, but  did  not  study  its  properties  extensively. 
1828;  4.     v.  Bonsdorff,  P.  A.     Beitrage  sur  Beantwortung  der 
Frage  ob  Chlor,  Jod  und  mehrere  andere  Metalloide, 


78  CHEMISTRY   OF   BERYLLIUM 

saueren  und  basenbilden  Korper  wie  der  Sauestoffe 
sind. 

Kongl.  Vet.  Acad.  Handl.,  1828,  174. 

Ann.  d.  Phys.   (Pogg),   17,   136. 

Made  a  double  chloride  of  mercury  and  beryllium  in 
rhombic  prisms,  but  gives  no  analysis  or  formula. 

1831 ;  i.     Berthemot.     Beitrage  sur     Geschicte     der     Bromure. 

Archiv.  der  Pharm.,  37,  332. 

J.  de  pharm.,  26,  649. 

Made  bromide  by  dissolving  BeO  in  HBr,  but  could  not 
crystallize. 

1831 ;    2.     Becquerel,    A.    C.     Considerations   generates    sur   les 
Decomposition    electro-chimique   et     la    Reduction     de 
1'oxide  de  fer,  de  la  zircon  et  de  la  magnesie,  a  1'aid  de 
forces  electrique  pen  energiques. 
Ann.  chim.  et  phys.,  48,  350. 
Pharm.  CentrbL,   1832,  527. 

Thought  he  reduced  by  the  current  BeCl2  which  was 
impure  with  iron,  but  could  not  reduce  pure  BeCl2. 

1831 ;  3.     Berzelius,  J.  J.     Ueber  das  Vanadin  und  seine  Eig- 
enschatten. 

Ann.   der   Phys.    (Pogg),  22,   58. 
Obtained    a    yellow,    neutral,    difficultly    soluble,    pow- 
dered beryllium  vanadate. 

1832;   i.     v.  Kobell,   Fr.   Vermuthung  iiber   die  Zusammenset- 
zung  der  Beryllerde. 

J.  fur  Chem.   (Schweigger),  64,  191. 

J.  prakt.  Chem.,   i,  92. 

Claims  that  while  CaCO3  will  precipitate  the  sesquiox- 
ides  in  the  cold,  it  will  not  throw  down  manganese,  zinc, 
iron  or  beryllium,  but  that  beryllium  is  thrown  out 
when  the  solution  is  heated  near  to  boiling.  Therefore, 
beryllium  is  bivalent. 


BIBLIOGRAPHY    OP    BERYLLIUM  79 

1833;   !•     Trommsdorff,  J.   B.       Ueber  die  Valeriansaure  und 
ihre   Verbindungen   Valeriansaure   Beryllerde. 

Ann.  der  Chem.   (Liebig),  6,  194. 

Ann.  der  Phys.  (Pogg),  29,  159. 

Pharm.  Centrbl.,   1832,  310. 

Beryllium  valerianate,  made  by  dissolving  carbonate 
in  acid,  dries  to  a  sweet,  gummy  mass,  unchangeable  in 
air.  (See  Lacombe,  1902). 

1833;  2.     Berzelius,  J.  J.     Untersuchung  iiber  die  Eigenschaft- 
en  des  Tellurs. 

Kongl.  Vet.  Acad.  Handl.,  1833. 

Ann.  der  Phys.  (Pogg),  32,  594,  607. 
Neutral  beryllium  tellurates  and  tellurites  were  precip- 
itated by  potassium  tellurate  or  tellurite  as  white  volu- 
minous flakes. 

1834;  i.     Balard,  A.  G.     Ueber  Verbindungen  des  Broms  mit 
Sauerstoff. 

J.  prakt.  Chem.,  4,  165. 

Pharm.  Centrbl.,  1835,  349. 

Bibl.  Univ.,  1834,  372. 

Claims  that  bromine  water  partly  dissolves  BeO  and  that 
light  has  an  apparent  influence  on  the  reaction. 
1834;  2.     Berzelius,  J.  J.     Ueber  die  Destinations  products  der 
Traubensaiire. 

Kongl.  Vet.  Acad.  Handl.,  1834. 

Ann.  der  Phys.   (Pogg),  36,  17.     . 

Pharm.  Centrbl.,  1836,  41. 

1837.   i.     Heller,  J.  F.       Rhodizonsaiire,  eine  neue  Oxidations 
stufe  des  Kohlenstoffes  und  die  Krokonsaiire. 

J.  prakt.  Chem.,  12,  227,  237. 

Pharm.  Centrbl.,  1837,  828,  833. 

Berzelius  Jsb.,  18,  521. 

Beryllium  rhodonate,  Be(H2C3O5),  is  a  brown  pow- 
der and  was  made  by  boiling  an  alcoholic  solution  of  the 
acid  with  beryllium  acetate.  Beryllium  krokonate, 
Be(HC5O4),  formed  in  yellow  crystals  was  made  same 
as  preceding. 


80  CHEMISTRY   OF   BERYLLIUM 

1858;  I.     Biot.  J.  B.     Des  combinations  fluides  formes  par  1'acide 
tartrique,  la  glucine  et  Teau. 

Comptes.  rend.,  6,   158. 

Used  a  tartrate  of  beryllium  made  by  Berthier  and 
found  specific  rotary  power  100  millimeters  to  be  + 
41.134  to  +43.992,  largest  of  any  tartrate  tried  (see 
1899;  13). 

1840;   I.     Gmelin,  L.       New  Methode  die  Beryllerde  von  der 
Thonerde  zu  trennen. 

Ann.  der  Phys.    (Pogg),  50,  175-181. 

Pharm.  Centrbl.,  2,  427. 

Berzelius  Jsb.,  21,  141. 

Ann.  der  Chem.,  36,  207. 

Ann.  des  mines,   (4)  2,  70. 

Chem.  Gaz.,  i,  9. 

Separates  iron,  beryllium  and  aluminum  as  follows: 
The  nearly  neutral  HC1  solution  is  precipitated  by  cold 
KOH  and  digested  in  excess  until  the  separated  Fe- 
(OH)3  has  a  clear  brown  color.  The  fluid  is  then  di- 
luted with  water  and  boiled  fifteen  minutes.  All  beryl- 
lium separates  out  carrying  some  iron.  Aluminum  is 
determined  in  filtrate.  Beryllium  precipitate  is  ignited, 
dissolved  and  retreated  to  remove  iron. 

1840;  2.     Schaffgotsch,  F.     Beitrage  zur  Kenntniss  der  Beryl- 
lerde. 

Ann.  der  Phys.   (Pogg),  50,  183-188. 

Pharm.  Centrbl.,  2,  438. 

Berzelius  Jsb.,  21,  95,  127,  141. 

Ann.  der  Chem.,  36,  206. 

Ann.  des  mines,   (4)   2,   170. 

J.  prakt.  Chem.,  (i)  20,  376. 

Phil.  Mag.,   (3)   21,  284. 

Chem.  Gaz.,  i,  9. 

Analyzed  the  hydroxides  and  gives  them  with  very 
doubtful  amounts  of  H2O.  The  carbonate  precipitated 
from  ammonium  carbonate  solution  and  dried  at  100° 
gave  47.53  per  cent.  BeO,  17.57  per  cent.  CO2,  34.90 


BIBLIOGRAPHY    OF    BERYIJJUM  8l 

per  cent.  H2O  (by  dif.).  Shows  some  relations  of 
Be(OH)2  to  KOH  as  Gmelin  (1840;  i)  and  may  have 
priority.  KOH  must  be  neither  too  strong  nor 
too  weak.  Says  precipitate  when  well  washed  with 
.H2O  is  again  soluble  in  KOH. 

1840,  3.     Scheerer,  T.     Untersuchung  des  Allanit,  Orthit,  Cer- 
in  und  Gadolinit. 

Ann.   der  Phys.    (Pogg),  51,  472. 
Was  unable  to  obtain  good  results  by  method  of  Gme- 
lin and  of  Schaffgotsch. 
1842;    i.     Rose,   H.     Die   Zusammensetzung   der  Beryllerde. 

Berichte  der  Akad.  der  Wis.  (Berlin),  1842,  138-141. 

J.  prakt.  Chem.,  27,  120. 

Berzelius  Jsb.,  22,   102. 

Preliminary  announcement  and  discussion  of  the  re- 
sults of  Awdejew  which  were  obtained  under  his  direc- 
tion. 

1842;  2.     Awdejew,  v.     Ueber  das  Beryllium  und  dessen  Ver- 
bindungen. 

Ann.  der  Phys.   (Pogg),  56,  100-124. 

Centrbl.,   13,   627. 

Berzelius  Jsb.,  23,  112  and  185. 

Ann.  d.  Chem.   (L,iebig),  44,  269. 

Ann.  de  chim.  et  phys.,   (3)   7,  155-173. 

Phil.  Mag.,  (3)  21,  284. 

Berg  u.  Hut.  Ztg.,  i,  830. 

Chem.  Gaz.,  i,  9. 

An  extended  and  valuable  research.  Found  the  con- 
ditions for  the  preparation  of  BeSO44H2O,  purified  it 
and  correctly  described  its  composition.  Was  the  first 
to  determine  the  atomic  weight  with  even  approximate 
accuracy.  Determined  atomic  weight  by  analysis  of 
sulphate.  Was  unsuccessful  with  chloride  on  account 
of  its  decomposition  by  water.  Discusses  the  question 
of  the  valency  of  Be  and  came  to  the  conclusion  that  it 
was  a  diad  mainly  from  a  study  of  the  double  salts  of 
beryllium  and  potassium.  Made  the  double  fluoride 


82  CHEMISTRY    OF   BERYLUUM 

2KF.BeF2.  Gave  the  symbol  BeCl2  to  the  chloride  and 
thought  he  made  BeCl2-{-4H2O  by  evaporation  in  vacuo 
which  is  undoubtedly  a  mistake. 

1842;  3.  Scheerer  Th.  Erste  Fortsetzung  der  Untersuchung- 
en  iiber  Gadolinit,  Allanit  und  damit  verwandte  Min- 
eralien. 

Ann.  der  Phys.   (Fogg),  56,  479. 

J.  prakt  Chem.,  27,  76  and  80. 

Centrbl.,   1843,  208. 

Berzelius  Jsb.,  23,  293. 

Chem.  Gaz.,   i,   177. 

Arch  de  pharm.,  29,  214. 

Read  at  Stockholm,  July  15,  1842. 

Separation  of  beryllium  from  iron.  Uses  ammonium 
sulphide  to  separate  the  small  amount  of  iron  dissolved 
by  ammonium  carbonate.  First  to  propose  this  sepa- 
ration. Did  not  obtain  good  results  by  Schaffgotsch 
method  of  separation. 

1843;  i-     R°se>  H.     Ueber  die  Ytterde. 

Ber.  der  Akad.  der  Wiss.  Berlin,  1843,  143. 

Ann.  der  Phys.  (Pogg),  56,  105. 
Separates  beryllium  from  yttrium  by  volatility  of  the 
chloride  on  treating  heated  oxides  mixed  with  carbon 
and  with  chlorine  gas.  The  residue  had  to  be  dissolved 
in  acid  precipitated  by  ammonia  and  three  times  ig- 
nited with  carbon  and  chlorine  to  remove  all  the  vola- 
tile chlorides,  but  these  chlorides  contained  no  yttrium. 

1843;  2-  Berthier,  P.  Sur  quelques  separations  operees  au 
moyen  de  1'acide  sulfureaux  en  des  sulfites  alcaline. 

Ann.  de  chim.  et  de  phys.,  (3)  7,  74. 

Ann.  der  Chem.   (Liebig),  46,  182. 

J.  prakt.  Chem.,   (i),  29,  68. 

Centrbl.,  1843,  378- 

Separates  ben-Ilium  from  aluminum,  cerium  and  yttri- 
um after  removal  of  most  of  the  aluminum,  as  alum, 
by  means  of  ammonium  sulphite  and  boiling  until  no 


BIBLIOGRAPHY    OF    BERYLLIUM  83 

more  SO,  comes  off.  Aluminum,  cerium  and  yttrium  are 
precipitated,  but  beryllium  remains  dissolved. 

1843;  3-  Damour,  A.  Nouvelles  analyses  sur  le  cymophane  de 
Haddam. 

Ann.  de  chim.  et  de  phys.,   (3)   7,  173. 

Centrbl.,  1843,  783- 

Discusses  the  formulas  BeO  and  Be2O3  as  applied  to 
cymophane  from  basis  of  Awde Jew's  work. 
1844;  J-     Bottinger,  Heinrich.     Ueber  die  von  Berthier  vorge- 
schlagene   Anwendung   der   schwefligen   Saure   in   der 
chemischen  Analyse. 

Ann.  der  Chem.   (Liebig),  51,  397. 
Attempted  to  make  quantitative  separation  of  beryllium 
and  aluminum   by   Berthier's   method  with   sulphurous 
acid,  but  invariably  found  beryllium  present  with  his 
aluminum. 

1845;  l-  Riess,  P.  Ueber  das  elektrische  Leitungsvermogen 
eineger  stoffe. 

Ann.  der  Phys.  (Pogg),  64,  53. 
1847;   I-     Peroz,  J.     Note  sur  les  pyrophosphates  doubles. 

Ann.  de  chim.  et  de  phys.,   (3)  20,  326. 
Simply  states  that  he  made  compounds  of  the  alkaline 
pyrophosphates  with  beryllium  pyrophosphate.  No  de- 
tails. 

1848;  i.  Play  fair,  Lyon  andn  Joule,  J.  P.  Researches  on  Atom- 
ic Voflume  and  Specific  Gravity. 

J.  Chem.  Soc.  (London),  3,  93. 

Discussion  of  relation  of    atomic    volume    to    specific 
gravity.     No  new  results. 

1848;  2.  Rose,  Heinrich.  Ueber  das  Specifische  Gewichte 
der  Thonerde,  der  Beryllerde,  der  Magnesia  und  des 
Eisenoxyds. 

Ber.  der.   Akad.  d.  Wiss.    (Berlin),   1848,   165-170. 

Centrbl.,  1848,  485. 

Ann.  der  Phys.   (Pogg),  74,  433- 

Jsb.  Chem.,  i,  398. 


84  CHEMISTRY   OF   BERYUJUM 

J.  prakt.  Chem.,  44,  226. 

llnst.  (Paris),  1848,  368. 

Ann.  der.  Chem.  u.  Pharm.  (Liebig),  68,  167. 
Beryllium  oxide  made  by  heating  the  basic  carbonate 
over  an  alcohol  lamp  showed  specific  gravity =3. 083- 
3.09.  By  heating  to  very  high  temperatures  in  por- 
celain oven  became  six-sided  crystals  and  specific  grav- 
ityr=3.o2i.  By  heat  hydroxide  precipitated  by  ammo- 
nia, specific  gravity = 3. 096.  Same  to  much  higher 
temperature,  specific  gravity =3. 027. 

1848;  3.     Rose,   Heinrich.     Ueber  die  Anwendung  des   Salmi- 
akes  in  der  Analytische  Chemie. 

Ber.  der.  Akad.  der  Wiss.  (Berlin),  1848,  202. 

Centrbl.,  (1848)  19,  602. 

J.  prakt.  Chem.,  45,  116. 

Ann.  der.  Phys.   (Pogg),  83,  145. 
Beryllium   carbonate,   oxide,   etc.,   are  only  partly   de- 
composed by  heating  with  ammonium  chloride. 
1850;    i.     Rivot,   L.   E.     De   Temploe  de   1'hydrogene  dans  les 
analyses  des  substances  minerales. 

Ann.  de  chim.  et  de  phys.,  (3)  30,  188. 

Ann.  Chem.  u.  Pharm.   (Liebig),  78,  212. 

J.  prakt.  Chem.,  51,  338. 

Centrbl.,   1850,  908. 

Jsb.  Chem.,  3,  599. 

Chem.  Gaz.,  9,  76. 

Separates  iron  oxide  from  beryllium  oxide  by  igniting 
in  hydrogen  and  dissolving  out  iron  in  dilute  nitric  acid 
(1-30)  or  determines  per  cent,  of  iron  from  loss  on 
ignition  in  hydrogen. 

1851 ;   i.     Ebelmen,  J.  J.     Recherches  sur  la  cristallization  par 
voie  seche. 

Comptes  rend.,  33,  526. 

Ann.  Chem.  (Liebig),  80,  211. 

Crystallized  beryllium  oxide  from  an  alkali  silicate  and 
obtained  six-sided  prisms  with  a  density  of  3.058.  Hard 
enough  to  scratch  glass,  insoluble  in  acids,  although 


BIBLIOGRAPHY    OF    BERYLLIUM  85 

slightly  in  hot  concentrated  H2SO4.  Easily  soluble  in 
HKSO4.  Claims  perfectly  isomorphous  with  crystals 
of  A12O3. 

1851;  2.  Ebelmen,  J.  J.  Ueber  die  Krystallization  auf  trock- 
nem  Wege. 

J.  prakt.  Chem.,  55,  342. 

Centrbl.,   1851,  529,   899. 

Jsb.   Chem.,   4,    15. 

1'Inst.   (Paris),  1851,  179,  369. 
Same  as  1851;  i,  but  separately  transmitted  by  author. 

1851;  3.  Ebelmen,  J.  J.  Sur  une  nouvelle  methode  pour  ob- 
tenir  des  combinaisons  cristallisees  par  la  voie  seche 
(sur  la  cymophane). 

Ann.  de  chim.  et  de  phys.,   (3)   33,  40. 
Made   cymophane   artificially   by   fusing  together   A12- 
O3,  BeO  and  B2O3. 

1853;  i.  Fremy,  E.  Recherches  sur  les  sulfures  decompos- 
ables  par  Teau;  suive  de  considerations  generates  sur 
la  production  des  eaux  sulfureuses  et  siliceuses. 

Comptes  rend.,  36,  178. 

Centrbl.,  1853,   113- 

Says  sulphide  of  beryllium  was  the  only  sulphide  he 
could  not  make  by  passing  CS2  over  hot  base. 
1853;  2.     Miiller,   EL     Mineralanalysen. 

J.  prakt.  Chem.,  58,  181. 

Several  analyses  of  beryl  with  methods  used  but  em- 
bodying nothing  new. 

1854;  i.  Weeren,  Julius.  Einige  Beitrage  zur  Kenntniss  der 
Beryllerde. 

Ann.  der  Phys.  (Pogg),  92,  91-128. 

J.  prakt.  Chem.,  62,  301. 

Ann.  Chem.    (Liebig),  92,  262. 

Centrbl.,  1854,  705. 

Jsb.  Chem.,  7,  336  and  728. 

Chem.  Gaz.,  12,  408. 
Amer.  J.  Sci.,  (2),  18,  414. 
An  extended  and  careful  research  on  beryllium.     De- 


86  CHEMISTRY   OF   BERYLLIUM 

termined  atomic  weight  by  ratio  BeO  :  SO3  in  care- 
fully purified  sulphate.  Compared  different  methods 
of  preparation.  Considered  methods  by  use  of  (NH4)2- 
CO3  and  by  NH4C1  best.  Gives  special  precautions  for 
latter. 

Studied  Be(OH)2  critically  and  gives  properties. 
Studied  carbonates  and  found  no  definite  composition, 
but  varying  proportions  of  carbonate  and  hydroxide 
according  to  treatment.  Gives  formulas  for  some  of 
these  as  obtained,  all  showing  a  high  ratio  of  base  to 
acid. 

Found  the  sulphate  lost  one  third  of  its  water  of  crys- 
tallization at  35 °C. 

1854;  2.     Debray,   Henri.       Du  glucyum  et  de  ses  composes. 
Academic  Dissertation,  Paris. 

Comptes  rend.,  38,  784. 

CentrbL,  1854,  44& 

Jsb.  Chem.,  7,  336. 

J.  prakt.  Chem.,  62,  180. 

Ann.  Chim.,   (Liebig),  92,  261. 

Chem.  Gaz.,  12,  204;  13,  386. 

Chemist,  I,  558. 

Arch,  ph.  nat,  26,   181. 

rinstitute,  (Paris),  1854-  142. 

Arch,  der  Pharm.,  142,  44. 

First  announcement  to  French  academy  of  results 
much  more  fully  described  in  1855;  i. 

1855;    *•     Debray,   Henri.     Du  glucinum   et  de   ses   composes. 
Academic  Dissertation,  Paris,   1855. 
Ann  de.  chim.  et  de  phys.,  (3),  44,  1-41. 

CentrbL,  1855,  549- 

Jsb.   Chem,  8,  356. 

Chem.  Gaz.,  13,  386. 

J.  Chem.  Soc.,  ( London),  8,  242. 

Extended  research.  Made  beryllium  by  reduction  of 
chloride  by  sodium  as  a  white  metal,  specific  gravity  2.1. 
and  describes  properties.  Could  not  make  the  sulphide 


BIBLIOGRAPHY    OF    BERYLLIUM  87 

as  Wohler  did.  Made  and  .described  BeO,  BeCl2,  BeI2, 
BeF2.KF,  BeSO4.4H2O,  K2SO.BeSO4.2H2O.  Made 
rather  indefinite  basic  carbonates,  obtaining  quantities 
equivalent  to  2Be(OH)2.BeCO3.3H2O  as  one  of  his 
products.  Also  made  double  carbonates  with  ammo- 
nium and  potassium.  Could  not  make  crystalline  oxal- 
ates  but  easily  prepared  the  double  oxalates,  BeC2O4. 
K2C2O4,  and  BeC2O4.(NH4)2C2O4.  Studied  the  prop- 
erties of  the  hydrate,  (Be(OH)2.  Decomposed  his 
beryl  by  fusing  with  lime.  Gives  a  new  method  of 
separation  from  aluminum  by  the  action  of  zinc  on 
mixed  sulphates,  hydrogen  being  evolved,  and  the  alu- 
minum precipitated  as  a  basic  sulphate.  Favored  bi- 
valency  of  beryllium. 

1855  >  2.     Rose,  Heinrich.     Ueber  des  Verhalten  der  verschie- 
denen    Basen    gegen   Losungen   amoniacalischer    Salze 
und  namentlich  gegen  die  Losung  von  chlorammonium. 
Ber.  Akad.  d.  Wiss.  (Berlin),  1855,  334- 
Centrbl.,  1855,  612. 

Found  that  beryllium  oxide  could  decompose  solutions 
of  ammonium  chloride  but  lost  this  property  when  very 
strongly  heated.  This  property  belongs  to  bases  RO 
and  not  R2O3. 

1855 ;  3.     Rose,   Heinrich.       Ueber  die  atomische   Zusammen- 
setzung  der  Beryllerde. 

Ber.  Akad.  d.  Wiss.  (Berlin),  1855,  581. 

Ann.   der  Phys.    (Pogg),  96,  445. 

J.  prakt.  Chem.,  64,  182. 

Centrbl.,  1855,  73°,  733- 

Jsb.  Chem.,  8,  361. 

1'Insntitute  (Paris),  1856,  in. 

Chem.  Gaz.,  13,  466. 

Discussion  of  previous  work,  (1848;  2)  and  concludes 
that  from  atomic  volume  considerations,  constitution 
of  oxide  must  be  R2O3  in  spite  of  results  with  ammo- 
nium chloride  (1855;  4). 


88  CHEMISTRY   OF   BERYLLIUM 

1857;   i.     Lewy,   B.     Recherches  sur  la  formation  et  la  com- 
position des  emeraudes. 
Cmptes  rend.,  45,  877. 

Concluded  color  of  emerald  was  due  to  organic  mat- 
ter and  not  to  chromium. 

1858;  i.     Ordway,  John  M.     Examination     of     soluble     basic 
sesqui  salts. 

Amer.  J.  of  Sci.,   (2)  26,  197. 
J.  prakt.  Chem.,  76,  22. 
Jsb.  Chem.,  n,  114. 

Discusses  the  formation  of  the  nitrate  but  finds  it 
very  difficult  to  crystallize.  Made  basic  compounds  by 
drying  solution  of  nitrate. 

1858 ;  2.     Lea,  M.  Carey.     On  picric  acid  and  some  of  its  salts. 

Amer.  J.  of  Sci.,  (2)  26,  382. 

Centrbl.,  1859,  I2I« 

Carbonate  of  beryllium  dissolves  readily  in  hot 
aqueous  picric  acid  and  by  evaporation  yields  golden 
yellow  crystalline  crusts. 

1858;  3.  Deville,  St.  Claire  and  Caron,  H.  Sur.  un  nuveau 
mode  de  production  a  1'etat  cristallise  d'une  certain 
nomber  d'especes  chimiques  et  mineralogiques. 

Comptes  rend.,  46,  765  . 

Chemist,  (3)  5,  5H- 

Fused  equal  equivalents  of  fluorides  of  aluminum  and 
beryllium  under  high  heat  in  boric  acid. 

1859;  l-  Hofmeister.  Uber  die  Trennung  der  Beryllerde  von 
der  Alaunerde,  nebst  der  Analyse  szweier  Beryll. 

J.  prakt.  Chem.,  76,  i. 

Rep.  chem.  pure,  i,  301. 

Jsb.  Chem.,  12,  675. 
Archiv.  der  Pharm.,  101,  177. 

Used  ammonium  carbonate  method  and  proposed  a 
number  of  fractional  precipitations  to  remove  all  alumi- 
num. 


BIBLIOGRAPHY    OP    B^RYUJUM  89 

1859;  2.     Ordway,  John  M.     Some  facts  respecting  the  nitrates. 

Amer.  Jour.  Sci.,  (2)  57,  18. 

J.  prakt.  Chem.,  76,  22. 

Solid  nitrate  of  beryllium  melts  as  low  as  140°  F., 
and  may  be  cooled  as  low  as  85 °F.,  before  it  begins  to 
solidify.  Boiled  as  low  as  285°F.,  continuing  to  boil 
and  remaining  clear  to  320° F.,  giving  off  acid  all  the 
time.  The  highly  basic  residue  did  not  solidify  on 
cooling  to  6i°F.,  on  adding  strong  nitric  acid  solidified 
and  temperature  rose  to  142°  F.  Dilution  with  a  "basic 
salt''  has  therefore  same  effect  as  dilution  with  H2O. 
1859;  3.  Scheffer,  G.  Beitrage  zur  Kenntniss  der  Beryllerde. 

Ann.  Chem.   (Liebig),  109,  144. 

J.  prakt.  Chem.,  77,  79. 

N.  arch.  ph.  nat.,  5,  180. 

Ann.  chim.  et  phys.,  (3)  56,  112. 

Rep.  chim.  pur.,  i,  317. 

Archiv.  der  Pharm.,  33,  144. 

Jsb.  Chem.,  12,  139. 

Le  Moniteur  scientifique,  2,  862. 

Phil.  Mag.,  (4)  18,  455- 

Scheffer  claims  to  have  decomposed  his  beryl  by  heat- 
ing in  a  lead  dish  at  100-200°  with  CaF2  and  concen- 
trated H2SO4.  Made  an  acid  phosphate,  BeHPO4. 
3H2O  which  on  drying  yielded  BeHPO4.H2O  and  a 
gummy  phosphate,  5BeO.2P2O5  +  8H2O  which  on  di- 
lution with  water  yielded  a  white  precipitate,  2BeO. 
Pa^5+5H2O.  These  results  are  interesting  as  -they  are 
quite  analogous  to  the  basic  sulphate  action  while  in 
reality  they  are  acid  compounds  if  phosphoric  acid  is 
tribasic.  Claimed  to  make  a  nitrate  by  evaporating 
BeO  and  HNO3  to  dryness  at  I2O°-I5O°.  Claimed  it 
then  lost  no  H2O  or  N2O5  (which  is  not  true  of  any 
nitrate  of  beryllium.  Obtained  first  class  results  by 
Debray's  method  of  separation  with  zinc.  By  precip- 
itating basic  beryllium  nitrate  with  Na4P2O7  obtained 
a  pulverulent  precipitate,  the  analysis  of  which  would 


9O  CHEMISTRY   OF   BERYUJUM 

yield  the  formula,  Be2P2O7.5H2O.  Made  a  triple  salt, 
BeNa2(NH4)2(PO4)27H2O  by  adding  NH4C1  be- 
fore precipitating  with  sodium  phosphate. 

1860;  i.  Cahours,  Aug.  Recherches  sur  les  radicaux  organo- 
metallique,  "Glucinium  ethyl." 

Ann.  chim.  et  phys.,  (3)  58,  22. 

Made  beryllium  ethyl  by  action  of  metallic  beryllium  on 
C2H51   in   sealed  tube.       Appeared   analogous   to   alu- 
minum ethyl,  but  did  not  have  enough  to  study. 
1861 ;  i.     Frankland,  E.     On  organo-metallic  bodies. 

J.  Chem.  Soc.   (London),  13,  181,  194. 
Discusses  briefly  conclusions  of  Cahours  (1860;  i)  on 
beryllium  ethyl. 

1862;  i.  Parkman,  Theodore.  On  the  carbonates  of  Alumina, 
Glucina  and  the  sesquioxides  of  Iron,  Chromium  and 
Uranium. 

Amer.  J.  of  Sci.,  (2)  34,  326. 

Centrbl.,  1863,  465,  468. 

Chem.  News,  7,  122. 

By  precipitating  BeSO4  with  Na2CO3  in  slight  excess 
he  obtained  a  basic  carbonate  containing  the  approxi- 
mate ratio  of  3BeO  :iCO2. 
1863;  i.     Joy,  Charles  A.     On  Glucinum  and  its  Compounds. 

Amer.  J.  of  Sci.,   (2)   36,  83. 

Chem.  News,  8,  183-197. 

J.  prakt.  Chem.,  92,  232. 

Jsb.  Chem.,  16,  676. 

Centrbl.,  1864,  1119. 

Bull.  soc.  chim.,  (2)  2,  351. 

An  extended  and  excellent  study  of  the  methods  of  de- 
composing beryl   and   separating   beryllium    from   alu- 
minum including  an  extended  bibliography  of  the  sub- 
ject and  of  the  minerals  containing  beryllium. 
Tried  the  following  methods  of  decomposing  beryl : 
i.  By    passing   chlorine    over   calcined    beryl,    oil    and 
lamp-black  in  hot  porcelain  tube.     Chloride  of  iron,  alu- 
minum and  beryllium  volatilized  together. 


BIBLIOGRAPHY    O*    BERYLLIUM  9! 

2.  By  treating  beryl  with  concentrated  HF  and  H2SO4. 
Claimed  to  succeed  if  beryl  was  very  finely  pulverized. 

3.  By  digesting  seven  parts  beryl,  13  parts  CaF2  in  18 
parts  H2SO4.     Decomposed  but  large  amount  of  cal- 
cium compounds  proved  a  great  disadvantage. 

4.  By  fusing  beryl  with  three  parts  of  KF  and  digest- 
ing with  H2SO4.     Fine  method  except  for  cost  of  KF. 
SiF4  is  driven  off  at  low  heat. 

5.  By  NH4P\  ditto. 

6.  By  digesting  in  H2SO4  and  fusing  with  potassium 
ferrocyanide  and  salt.     Complete  failure. 

7.  By  fusing  with  CaF2.     Attacked  crucible  badly  and 
large  amount  of  calcium  compounds  caused  complica- 
tions. 

8.  By   fusing  two  parts  beryl   with   one  part  CaO   in 
Hessian  crucible.     Attacked  crucible,  but  claimed  de- 
cided advantages  if  suitable  crucible  could  be  found. 

9.  By    fusing   with   litharge.        Not   so   good   as   with 
K2C03. 

10.  By  fusing  with  MnO2.     Decomposed  but  no  advan- 
tage. 

11.  By  fusing  a  mixture  of  two  parts  Na2CO3  and  three 
parts  K2CO3.     Worked  well,  but  preferred  the  follow- 
ing. 

12.  By  fusing  one  part  beryl  with  two  parts  K2CO3. 
Preferred   this   method   to   any   of  the   others.     Fused 
mass  decomposed  with  H2SO4,  evaporated  to  get  rid 
of  silica,  crystallized  out  alum,  etc. 

Joy  also  tried  the  following  for  separating  beryllium 
from  aluminum : 

1.  By  NH4C1.     Precipitated  by  NH4OH  and  digested 
in   concentrated   solution   of   NH4C1   with   addition   of 
evaporated   water.     Iron   and  aluminum   remain  insol- 
uble and   beryllium   goes   into   solution.     Tedious,   but 
accurate. 

2.  By   carbonate   of   ammonium.     Some   aluminum   al- 
so goes  into  solution,  although  it  does  not  when  alone. 


92  CHEMISTRY   OF   BERYUJUM 

3.  By  caustic  potash.     Mixed  solution  in  HC1  is  pre- 
cipitated with  KOH  which  is  gradually  added  in  ex- 
cess  until   precipitate   dissolves,   then   diluted   with    10 
volumes  of  water   and  boiled.     Beryllium   precipitates 
partially  and  fairly  free  from  aluminum  and  iron,  but 
much  loss  of  beryllium. 

4.  By  sulphurous  acid.     Did  not  succeed  as  some  ber- 
yllium was  always  thrown   down  with  the  basic  sul- 
phite of  aluminum. 

5.  By  BaCO.,.     Both  precipitated. 

6.  By  Na2S2O3.     Both  precipitated. 

7.  By  decomposing  the  nitrates  heated  to  200  to  250. 
Both  acted  the  same. 

8.  By  acetate  of  soda.     Beryllium,  aluminum  and  iron 
act  the  same. 

9.  By  fusion  with  KOH.     Act  alike. 

10.  By   ammonium    formate.     Act   alike. 

11.  By  decomposition  of  sulphates.     Act  alike. 

12.  By  formation  of  alum.     Considers  this  best. 
1864;   I-     Wohler,   F.,  and  Rose,   G.     Sur  la  nature  colorante 

des  emeraudes. 

Comptes  rend.,  58,  1180. 

Chem.  News,  10,  22. 

Deny  coloring  matter  of  emerald  due  to  organic  mat- 
ter and  heated  to  prove.  Imitate  color  in  glass  by  a 
small  amount  of  chromium. 

1864;  2-  Gibbs,  Wolcott.  On  the  quantitative  separation  of 
cerium  from  yttrium,  aluminum,  glucinum,  manganese, 
iron  and  uranium. 

Amer.  Jour,  of  Sci.,   (2)  37,  354- 

J.  prakt.  Chem.,  94,  121. 

Chem.  News,  10,  195. 

Ztschr.  f.  Chem.,  1865,  15. 

Separates  beryllium  from  cerium  group  by  its  solubil- 
ity in  saturated  sodium  sulphate ;  from  yttrium  group  by 
oxalate  of  ammonia. 


BIBLIOGRAPHY    Otf    BERYLLIUM  93 

1864;  3.     Gibbs,  Wolcott.     On  the  employment  of  fluohydrate 
of  fluoride  of  potassium  in  analysis. 

Amer.  J.  of  Sci.,  (2)  37,  356. 

CentrbL,   1864,  990. 

Jsb.  Chem.,  17,  684. 

J.  prakt.  Chem.,  94,  121. 

Ztschr.  f.  Chem.,  1865,  16. 

Chem.  News,  10,  37  and  39. 

Bull.  soc.  chim.,  (2)  4,  359. 

States  that  fusing  crude  BeO  with  HF.  KF  and  treat- 
ing the  fused  mass  with  boiling  water  and  slight  amount 
of  HF  and  recrystallization  is  the  best  known  (1864) 
method  of  producing  a  chemically  pure  salt  of  beryl- 
lium. Under  these  conditionss  the  aluminum  is  sepa- 
rated as  the  very  insoluble  A1F3  ;3KF.  Also  states  that 
NaF  precipitates  the  aluminum  probably  quantitative- 
ly from  a  mixture  of  the  fluorides  of  aluminum  and 
beryllium. 

1864;  4.     Gibbs,  Wolcott.     Beitrage  zur  Chemie  aus  dem  Lab- 
oratorium  der  Lawrence  Scientific  School. 

Ztschr.  anal.  Chem.,  3,  397,  399. 

Same  as  1864,  2  and  3. 
1865;   i.     Delafontaine,   Marc.     Metals  in  Gadolinite. 

Chem.  News,  u,  159. 

Archiv.  d.  sci.  phys.  and  nat.  Geneva,  97,  101. 
1866;  i.     Cooke,  J.  P.     On  Danalite,  a  New  Mineral  Species 
from  the  Granite  of  Rockland,  Mass. 

Amer.  J.  Sci.,  (2)  42,  78. 

Ztschr.  anal.  Chem.,  6,  226. 

Gives  method  of  analysis  and  discusses  method  of  St. 
Clair  Deville  (Annales.,  38).  Says  it  is  one  of  the  most 
accurate  in  analytical  chemistry.  Separates  beryllium 
from  iron  by  reducing  iron  in  platinum  tube  in  a  cur- 
rent of  hydrogen  and  then  volatilizing  in  a  current  of 
HC1.  Aluminum  and  beryllium  not  effected.  See  1850, 
Rivot. 


94  CHEMISTRY   OF   BERYLLIUM 

1866;  2.     Hermes,  O.     Beitrage  zur  Kenntniss  der  Schweifel- 
cyan  verbindungen. 
J.  prakt.  Chem.,  97,  475. 
CentrbL,  1867,  112. 

Made  Be(CyS)2  by  action  of  H(CyS)  on  carbonate. 
Soluble  in  alcohol.  Salt  poorly  defined  and  doubtful. 

1867;  i.     Debray,  H.     Report  to  the  Societe  chimique  de  Paris 
on  beryllium  on  exhibition  at  the  Paris  Exposition. 

Bull.  soc.  chim.,   (2)   7,  465. 

Simple  statement  (no  details)  that  Debray  reported  on 
metallic  beryllium  exhibited  at  the  Paris  exposition, 
which  was  manufactured  by  M.  Menier  by  heating  with 
sodium,  a  mixture  of  BeCl2  and  the  double  fluorides  of 
beryllium  and  potassium  in  a  crucible  of  pure  alum- 
inum. 

1869;  I.     Klatzo,  Georg.     Die  Constitution  der  Beryllerde. 

Academic  Dissertation,  Dorpat. 

Ztschr.  f.  Chem.,  12,  129. 

Centrbl.,    1869,  832. 

Bull.  soc.  chim.,  (2)  12,  131. 

N.  arch.  phys.  nat,  34,  354. 

Jsb.  Chem.,  12,  203;  13,  256. 

J.  prakt.  Chem.,  106,  227-244. 

Tids.  for  Phys.  og.  Chem.,  8,  167. 

Ztschr.  anal.  Chem.,  8,  202  and  523. 

Chem.  News,  19,  227. 

J.  Frank.  Inst.,  89,  260. 

An  extended  article  full  of  erroneous  work  as  shown 
by  Marignac  and  others.  Studied  sulphates  and  claimed 
to  make  a  new  sulphate,  BeSO4.7H.,O. 
By  saturating  the  basic  carbonate  with  CO2  in  water  and 
evaporating  in  an  atmosphere  of  CO2,  he  claimed  to 
obtain  crystals  of  BeCO34H2O  which  formed  double 
salts  with  alkaline  carbonates. 

By  precipitating  ammonium  carbonate  solution  with  al- 
cohol, claimed  to  make  the  compound  3BeCO3.BeO, 


BIBLIOGRAPHY    OF    BERYLLIUM  95 

H2O+3(NH4)2CO8.     Made  a  basic  carbonate  of  for- 
mula similar,  to  that  obtained  by  Debray. 
Determined  the  atomic  weight  by  ignition  of  sulphate. 
Studied  the  chloride  and  fluoride. 

1869;   2.     Thalen,   Rob.        Memoire   sur   la   determination  des 
lonqueurs  d'onde  des  raies  metalliques. 

Nova  Acta  Reg.  Soc.  Sc.  Upsal.  (3)  vol.  6. 

Ann.  chim.  et  phys.,  (4)   18,  228. 

Found  the  wave  length  of  the  bright  rays  of  the  Beryl- 
lium spectra  to  be  4572  in  the  blue  and  4488.5  in  the 
indigo. 
1870;  i.     Thomsen,  Julius.     Ueber  Berylliumplatinchlorid. 

Berichte,   1870,  827. 

Centrbl.,  1870,  690. 

Jsb.  Chem.,  1870,  318. 

J.  Chem.  Soc.   (London),  24,  202. 

Bull.  soc.  chim.,  (2)   15,  50. 

Ztschr.  f.  Chem.,  14,  46. 

Chem.  News,  22,  263. 

J.  Applied  Chem.,  5,  185. 
Made  BePtCl6.8H2O. 

1871;  i.     Thomsen,   J.     Die   Warmeentwickelung   der   Neutra- 
lization. 

Ann.  der  Phys.   (Pogg),  143,  497. 

Berichte,  4  (1871),  586. 

Bull.  soc.  chim.,   (2)   16,  63. 

Jsb.  Chem.,  1871,  102. 

Determined  among  many  others,  the  heat  of  neutraliza- 
tion of  Be  (OH) 2  with  sulphuric  and  hydrochloric  acid. 
Found  Be(OH)2  +  H2SO4+Aq=  16100,  Be(OH)2  + 
2HCl-}-Aq=:  13640. 

1871 ;  2.     Toczyknski,    F.     Ueber    die   Platincyanide   und   Tar- 
trate  des  Beryllium. 

Ztschr.  f.  Chem.,  15,  275.. 

Inaugural  Dissertation,  Dorpat,  1871. 

Bull.  soc.  chim.,  (2)  16,  254. 

Centrbl.,  1871,  564;  1872,  517. 

Jsb.  Chem.,  1871,  286,  359. 


96  CHEMISTRY   OF   BERYUJUM 

Pharm.  Ztschr.  f.  Russl.,  n,  166,  204. 

J.  Chem.  Soc.  (Lon.),  24,  1013. 

Chem.  News,  24,  158. 

Made  green  ferrocyanide  of  Beryllium  by  precipitating 
barium  salt  with  BeSO4.  Made  ferricyanide  by  oxidiz- 
ing ferrocyanide  with  Cl,  olive  green.  Could  not 
separate  the  sulphocyanate  and  nitroprusside. 
Made  BePtCy4+4H2O  by  precipitating  barium  salt  in 
crystals,  changing  on  heating  through  gold,  yellow, 
orange  red. 

Made  BeMg2Pt3Cy12.i6H2O  by  crystallizing  the  two 
cyanides  together. 

Made  several  very  complicated  and  basic  double  tar- 
trates  to  which  he  gave  formulas. 

1872;  i.     Topsoe,  Haldor.     Krystallographische-chemische  Un- 
tersuchungen. 

Stizber.  d.  k.  Akad.  Wiss.  Wein,  66,  II,  5. 

Jsb.  Chem.,  1872,  163. 

N.  arch.  sci.  phys.  nat.,  45,  (1872),  76. 
BeSO44H2O,   tetragonal   a  :  c  =  1 10.9461 .       Observed 
form    (on). (no)    uniaxial,   negative,   specific  gravity 

1725- 

BeSeO4.4H2O,  at  100°  loses  two  molecules  H2O,  spe- 
cific gravity  2.029.  Rhombohedral,  a  :b  :c=i  10.9602: 
0.90275.  Observed  forms  (oil).(lOl).(O2l).(lIl). 
(ooi). 

Also  made  isomorphous  mixtures  of  the  sulphate  and 
selenate  and  studied  crystals  of  same. 

1873;    i.     Cahours,   A.     Recherches    sur   de   nouveaux   derives 
du  propyle. 

Comptes  rend.,  76,  1383. 

Centrbl.,  1873,  482. 

Jsb.  Chem.,  1873,  520. 

Berichte,  6,  821. 

J.  Chem.  Soc.  (London),  26,  871. 

J.  Russ.  Phys.  and  Chem.  Soc.,  5,  274. 
Made  beryllium  propyl  by  acting  on  mercury  propyl  at 


BIBLIOGRAPHY    OF    BE)RYIJJUM  97 

130-135°  in  sealed  tube.  Beryllium  propyl  was  dis- 
tilled in  atmosphere  of  CO2  to  a  colorless  liquid  boil- 
ing at  244-246°.  Fumes  in  air  and  is  spontaneously 
combustible.  Thick  oil  at  17°.  Decomposed  by  H2O. 
Also  confirms  earlier  experiments  1860;  i  on  beryllium 
ethyl  and  prepared  same  in  like  manner  to  above  with 
boiling  point  185-188°  and  properties  similar. 

1873;  2.  Marignac,  C.  de.  Notices  chimiques  et  cristallogra- 
phiques  sur  quelques  sels  de  glucine  et  des  metaux  de 
la  cerite. 

N.  arch.  d.  sci.  phys.  nat.,  46,  193. 

Ann.  chim.  et  phys.,  (4)  30,  45-69. 

Jsb.  Chem.,  1873,  259. 

Chem.  News,  28,  45. 

J.  Chem.  Soc.   (London),  27,  24. 

J.  Russ.  Phys.  and  Chem.  Soc.,  5,  II,  303. 
Confirms  Awdejew  (1842;  2)  2KF.BeF2  and  made  also 
KF.BeF2,  2NaF.BeF2,  NaF.BeF2,  2NH4F.BeF2.  Con- 
firms K2SO4.BeSO4.2H2O.  Concluded  that  beryllium 
is  not  isomorphous  with  Al  or  Mg  group.  Gives  forms 
of  crystals  and  finds  many  differences  from  Klatzo, 
(1869;  i). 

1873;  3.  Williams,  C.  Grenville.  Researches  on  Emeralds  and 
Beryls.  I.  On  the  coloring  matter  of  the  emerald, 

Phil.  Mag.,  (4)  46,  314. 

Proc.  Roy.  Soc.,  21,  409. 

Fused  emeralds  and  beryls  in  oxyhydrogen  blow-pipe 
and  made  artificial  emeralds  and  beryls  by  simply  fus- 
ing constituents  together.  Concluded  coloring  matter 
to  be  due  to  chromic  oxide. 

1873;  4.  Thomsen,  Julius.  Untersuchung  uber  die  Warmton- 
ung  beim  Auflosen  verscheidener  fester  fliissiger  und 
liiftformiger  Korper  in  Wasser. 

Berichte,  6,  712. 

By  dissolving  one  molecule  BeSO44H2O  in  400  mole- 
cules of  water,  found  heat  of  solution  =  -f-  1 100. 


9§  CHEMISTRY   OF   BERYLLIUM 

1873;  5.     Welkow,  A.     Beryllium  Platinchloride. 
Berichte,  6,  1288. 
Centrbl.,  1874,  50. 
Bull.  soc.  chim.,  (2)  21,  273. 
Amer.  Chem.,  4,  390. 
Jsb.  Chem.,  1873,  258. 
J.  Chem.   Soc.    (London),  27,  229. 
Chem.  News,  29,  51. 

Made  BePtCl0.8H2O,  tetragonal,  dark  yellow  crystals 
see  Thomsen,  1870;  i. 

1873;  6.  Topsoe,  Haldor.  Tabelle  iiber  die  specifischen  Gew- 
ichte,  Moleculargewichte,  und  Molecularvolumen  ver- 
schiedene  Salze. 

Centrbl.,  1873,  76. 

Contains  summary  of  his  work  1872;  I  and  also  calcu- 
lates molecular  volume  from  data  then  given. 
1873;  7.     Atterberg,  Albert.       Undersokningar  ofver  Metallen 
Berylliums  Foreningar. 

Kongl.    Svenska    Vetenskaps-Akademiens. 

Handlingar,  12,  1-38. 

Chem.  Centrbl.,  1874,  33O. 

Berichte,  7,  472. 

Atterberg  especially  calls  attention  to  the  tendency  of 
beryllium  to  form  substances  of  a  highly  basic  nature 
and  claims  to  have  made  the  following  compounds: 
Be(OH)2. 
3Be(OH)2.H20, 
3Be(OH)2.7H20. 
BeS04.2H20, 
BeSO4.4H2O, 
BeSO4.Be(OH)2.2H2O, 
BeSO4.2Be(OH)2.2H2O, 
BeSO4.7Be(OH)2.2H2O, 
BeK2(SO4)2.2H2O, 
BeK2  ( SO4 )  2-f  2KHSO4+4H  A 
3BeSO4.2Na2SO4.i2H2O, 
BeS04.(NH4)2S04.2H20, 


BIBLIOGRAPHY    Otf    BERYUJUM  99 

BeSe04.4H2O, 
BeS03.Be(OH)2.2H2O, 
BeSeO3.H2O, 

2(BeSeO3.H2O).Be(OH)2, 
2BeSeO3.Be(OH)2.5H2O, 
BeSeO3.Be(OH)2.H2O, 
BeSe03.Be(OH)2.3H2O, 
BeCrO4.i3Be(OH)2+ioH2O, 
BeMoO4.Be(OH)2-f2H2O, 
BeMoO4.MoO3.H2O, 
2BeCl2.3HgCl2.6H2O, 
BeC4H4O4.2H2O  (succinate), 
BeC4H4O4.Be  ( OH  )  2.2H2O, 
BeCl2.4H2O, 
BeCl2.3Be(OH)2, 
BeCl2.i2Be(OH)2-f-ioH2O, 
BeCl2.SnCl4.8H2O. 
BeCl2.AuCl3, 
Be(C104)2.4H20, 
Be3(104)2+iiH20+i3H20, 
Be3(P04),7H20, 
BeC2O4.Be(OH)2.H2O, 
BeC2O4.6Be(OH)2.6H2O, 
BeC4H406.3H20, 

Many  of  which,  in  fact,  have  no  existence  as  definite 
compounds. 

1873;    8.     Atterberg,   A.     Faits    pour   servier   a   Thistoire   der 
glucinium. 

Bull.  soc.  chim.,  19,  497. 

Jsb.  Chem.,  1873,  257. 

Chem.  Centrbl.,  1873,  53O- 

J.  Chem.   Soc.   (London),  26,   1003. 

J.  Russ.  Phys.  and  Chem.  Soc.,  5,  II,  303. 
Separately  transmitted,  but  contains  nothing  not  in  1873  ; 
7,  except  BeSO4.5Be(OH)2.2H2O. 

9.     Topsoe,  H  and  Christiansen,  C.     Recherches  optiques 
sur  quelques  series  de  substances  isomorphes. 


TOO  CHEMISTRY  OF  BERYLLIUM 

Ann.  chim.  et  phys.,  (5)  I,  5. 

Complete  from  Vidensky,  Selsk.,  1873,  9,  625. 

Ann.  der  Phys.  (Pogg),  Erganz-Bd.,  6,  499. 

Chem.  Centrbl.,  1874,  258. 
BeSO44H2O,  optically  negative. 
Tetragonal  a  :c=i  10.9461. 
Mean  values  indices  of  refraction. 

C  =--1.4374  0=1.4691 

e       D=  1.4395  w          D  =1.4720 

F  =  1.4450  F  =1.4779 

BeSeO44H2O,  rhombohedral.    a  :b  :c=  i  '.0.9602  -.0.9027. 
Mean  indices. 

V-a  P-b  V* 

c   1.4992     1.4973     1.4639 

D          1.5027  1.5007  1.4664 

F  1.5101  1.5084  1.4725 

1873;  10.     Hoist,  N.  O.     Bidrag  till  Kannedomen  om  Platinas 
Cyanforeningar. 

Ars-skrift.  Univ.  Lund.,  10,  II,  No.  6. 

Bull.  soc.  chim.,  (2)  22,  349. 

Chem.  Centrbl.,  1874,  786. 

Benchte,  8,  125. 

Jsb.  Chem.,  1875,  238. 
Made  the  salt  BePtBr2Cy4  in  crystals. 
1874;  I.     Atterberg,  Albert.  Sur  les  combinaisons  du  glucinium. 

Bull.  soc.  chim.,  (2)  21,  157. 

Berichte,  7,  472. 

J.  Chem.  Soc.  (London),  27,  658. 

Ztschr.  anal.  Chem.,  13,  316. 

J.  Russ.  Chem.  and  Phys.  Soc.,  6,  II,  84. 
Separately    transmitted,    but   contains    nothing   not   in 

1873;  7- 

1874;  2.     Thomsen,  J.     Die  Neutralizationswarme  der  oxyde  des 
Lanthans,  Ceriums,  Didyms,  Yttriums  and  Erbium. 

Berichte,  7,  33. 

Uses  his  previously  obtained  figures   for  Be(OH)2  in 
discussion. 

1874;  3.     Welkow,  A.     Beryllium-Palladiumchlorid. 
Berichte,  7,  38. 


BIBLIOGRAPHY  OF  BERYLLIUM  IOI 

Chcm.  Centrbl.,  1874,  5°,  245. 

Jsb.  Chem.,  1874,  254. 

J.  Chem.  Soc.  (London),  27,  443. 

Amer.  Chem.,  4,  469. 

Chem.  News,  29,   155. 

Gaz.  chim.  ital.,  4,  278. 

Bull.  soc.  chim.,  2,  (21)  273. 

Made  BePdCl6+8H2O,  dark  red  brown  crystals,  loses 
all  of  its  water  at    130°.     Isomorphous    with    BePd- 
C16+8H20. 
1874;  4.     Thomsen,  J.     Beryllium-Platinchlorid. 

Berichte,  7,  75. 

Chem.  Centrbl.,  1874,  245. 

Note  to  the  effect  that  he  had  priority  over  Welkow  and 
that  Marignac  had  corrected  his  9H2O  to  8H2O  which 
he  found  correct. 

1874;  5.     Welkow,  A.     Aluminum-Platinchlorid. 

Berichte,  7,  306. 

Bull.  soc.  chim.,  (2)  22,  153. 

Gaz.  chim.  ital.,  4,  302. 

Chem.  Centrbl.,  1874,  292. 

States  that  his  comparisons  with  the  beryllium  salt  show 
no  crystallographic  resemblance  and  does  not  lead  to 
placing  Be  in  Al  group. 
1874;  6.     Welkow,  A.     Beryllium- Palladiumchloriir. 

Berichte,  7,  803. 

Chem.  Centrbl,  1874,  476. 

Jsb.  Chem.,  1874,  254. 

J.  Chem.  Soc.  (London),  27,  1065. 

Amer.  Chemist,  5,  264. 

Bull.  soc.  chim.,  (2),  22,  499. 

Gaz.  chim.  ital.,  5,  61. 

By  heating  cone,  solution  of  BePdCle-SH^O  chlorine  is 
evolved  and  BePdCl4.6H2O  left  in  soluble,  brown 
tabular  crystals.  Also  obtained  a  double  iodide  of  Be 
and  Sb,  and  Be  and  Bi  which  were  so  unstable,  he  could 
not  assign  a  satisfactory  formula,  but  found  no  re- 


102  CHEMISTRY  OF   BERYLUUM 

semblance  to  corresponding  Al  compound.  Could  not 
make  double  chlorides  with  alkali  metals. 

1875;  I.     Bunsen,  R.  W.     Spectral  Analytische  Untersuchung. 
Ann.  d.  Phys.  (Pogg),  155,  230,  366. 
Ztschr.  anal.  Chem.,  15,  92. 
Short  reference  to  spectra  of  Be. 

1875;  2.     Nilson,  L,.  F.     Zur  Frage  iiber  die  Valenz  der  selten 

Erdmetalle. 

Berichte,  8,  655. 

Chem.  Centrbl.,  1875,  449. 

Claims  to  have  made  the  following  salts,  5BeO.2SeO2+ 
ioH2O,  BeSeO3.2H2O,  BeSeO3H2SeO3,  BeSeO3.2H2- 
SeO3,  which,  he  says,  indicate  the  BeO  rather  than 
Be2O3  formula. 

1875;  3.     Nilson,  L.  F.     Recherches  sur  les  selenites. 

Nova  Acta  reg.  Soc.  Sci.  Upsala  1875,  transmitted  by 
Cleve  to  Bull.  soc.  chim.,  (2),  23,  355. 
Same  as  1875 ;  2,  but  separately  transmitted  and  con- 
tains besides  those  enumerated  there, 
5Be0.8SeO2.5H2O, 
3Be0.7Se02.5H20. 

1875;  4.     Atterberg,  A.     Nagra  Ytterligare  bidrag  till  Kanne- 
domen  om  Beryllium  foresingarna. 

Ofvrvsgt.  Kongl.  Vet.  Akad.  Forhand,  1875,  No.  7,  32. 

Hull.  soc.  chim.  (2),  24,  358. 

Chem.  Centrbl,  1876,  35. 

Berichte,  9,  856. 

Jour.  Chem.  Soc.   (London),  30,  382. 

Gaz.  chim.  ital.,  6,  159. 

Communicated  through  M.  Cleve,  prepared  BeCl2. 
2(  (C2H5)2O).  Claims  that  his  previously  given 
formula,  3BeCl2.2Be(OH)2,  was  incorrect  and  should 
be  BeO.HCl. 

Also  made  BeHPO4.3H2O,  Be3(PO4)2.  6  or  7  H2O4 
Be8(AsO4)2.6H2O, 
BeHAsO4.2H2O. 


BIBLIOGRAPHY  OF  BERYLLIUM  IO3 

1876;  I.  Nilson,  L.  F.  Zur  Frage  iiber  die  Valenz  der  seltenen 
Erdmetalle. 

Berichte,  9,  1056,  1145. 

Jsb.  Chem.,  1876,  292. 

Bull.  soc.  chim.   (2),  27,  206. 

J.  Russ.  Phys.  and  Chem  Sec.,  9,  II,  98. 

Amer.  Chemist,  7,  242. 

J.  prakt.  Chem.,  15,  177. 

Discusses  the  work  of  others  on  BePtCl6.8H2O,  and 
makes  BePtCl4.5H2O.  Again  places  Be  in  divalent 
metals. 

1876;  2.  Nilson,  L.  F.  Untersuchung  iiber  Chlorosalze  tmd 
Doppel  nitrite  des  Platins.  (Beryllium  plato  and  di- 
platonitrite). 

Nov.  Acta.  Soc.  Sci.  Upsala  (3)  vol.  extra,  (1877), 
number  15.  Ofvst.  Akad.  Handl.  (Stockholm),  33, 
number  23. 

Berichte,  9,  1722. 

J.  prakt.  Chem.   (2),  16,  264. 

Chem.  Centrbl.,  1878,  211. 

Chem.  News,  34,  270;  37,  31. 

Jsb.  Chem.,  1876,  295,  1877,  31°- 

Bull.  soc.  chim.   (2),  27,  210,  245. 
Treated  BeSO44H,O  with  barium  plato  nitrite,  filtered 
and  evaporated  in  vacuum.     Obtained  Be(2NO2.Pt)2.- 
O.9H2O  (diplatonitrite),  but  could  not  make  the  plato- 
nitrite.     Makes  BePtCl4+5H,O. 

1876;  3.  Reynolds,  J.  Emerson.  On  Glucinum,  its  atomic 
weight  and  specific  heat.  (Read  April  TO,  1876). 

Phil.  Mag.,  (5)  3,  38-42. 

Bull.  soc.  chim.,  (2)  28,  161. 

Chem.  Centrbl.,  1877,  210. 

Chem.  News,  35,  119. 

J.  Chem.  Soc.   (London),  31,  579. 

Berichte,  9,  1806. 

J.  Russ.  Phys.,  and  Chem.  Soc.,  9,  II,  244. 
Reduced  BeCl2,  made   from  beryl,  by  Na  in  platinum 
crucible  below  fusion  and  determined  specific  heat  com- 


104  CHEMISTRY   OF   BERYIJJUM 

pared  to  siver  in  special  calorimeter.     Found   specific 
heat  =  0.642  at   TOO°,  at.   heat   5.91.     Concluded  at. 
wt.  therefore  to  be  9.2. 
1877;  i.     Williams,  C.  Grenville.     Researches  on  Emeralds  and 

Beryls.     II. 

Chem.  News,  35,  257. 

Analysis  and  study  of  separation  of  Be  and  Al.  Noth- 
ing especially  new. 

1877;  2.     Cossa  and  Pecile.     Einwirkung  von  Fluormagnesium 
auf  des  sulphate  des  Aluminums  und  Berylliums. 

Berichte,  10,  1099. 
Formed  fluoride  of  both  metals. 
1878;  i.     Smith,  Edgar  F.     Beryll  um  borate. 

Proc.  Amer.  Chem.  Soc.,  2,  114. 

Found  that  if  BeCl2  was  precipitated  with  excess  of 
borax  and  precipitate  washed  with  hot  water,  only 
Be(OH)2  was  left 

1878;  2.     Nilson,    L.    F.    and    Pettersson,    Otto.       Ueber    die 
specifische  Warme  des  Berylliums. 

Berichte,  n,  381. 

Tids  Krift,  17,  109. 

Short  report  to  German  Chem.  Soc.  of  1878;  3  and 
1878;  4. 

1878;  3.     Nilson,  L.  F.  and  Pettersson,  Otto.     Ueber  Darstel- 
lung  und  Valenz  des  Berylliums. 

Ann.  der  Phys.  (Wied),  4,  554-5^5- 

Nova  Acta.  Soc.  Sci.  Upsala,  10,  (1879),  number  9, 

Chem.  Centrbl.,  1878,  275,  610. 

Jsb.  Chem.,  1878,  70,  241. 

Amer.  Jour.  Sci.  (3),  15,  386;  16,  384. 

Chem.  News.,  37,  225. 

Very  complete  article.  Historical  review,  preparation 
of  (87  per  cent.)  metal  by  decomposition  of  chloride  by 
sodium.  Fused  metal  under  salt  in  closed  iron  crucible. 
Properties  of  metal  and  list  of  "all  well  characterized'1 
compounds  made  up  to  that  time.  List  contains  many 
of  very  doubtful  composition  and  omits  some  that  prob- 


BIBLIOGRAPHY  OF  B£RYWJUM  105 

ably  do  exist.  Concluded  Be  to  be  trivalent.  Specific 
gravity  Be=i.64,  specific  heat  at  6°  =0.2471.  Could 
not  make  sulphide. 

1878;  4.  Nilson,  L.  F.  and  Pettersson,  Otto.  Sur  ies  prop- 
rieties physiques  et  sur  la  chaleur  specifique  de  glucin- 
ium. 

Comptes  rend.,  83,  823. 

Ann.  die  chim.  et  de  phys.  (5),  14,  426. 

Bull.  soc.  chim.  (2),  31,  442. 

Separately  presented  by  M.  Berthelot.  Complete  in 
Annales.  Same  as  1878;  3. 

1878;  5.  Meyer,  Lothar.  Ueber  das  Atomgewicht  des  Beryl- 
liums. 

Berichte,  n,  576. 

Chem.  Centrbl.,  1878,  370. 

Chem.  News,  38,  9. 

J.  Chem.  Soc.  (London),  34,  557. 

J.  Russ.  Phys.  and  Chem.  Soc.,  n,  II,  40,. 
Discusses  1878;  3  and  4  and  questions  conclusion  that 
Be  is  trivalent. 
1878;  6.     Brauner,  B.  •  Ueber  das  Atomgewicht  des  Berylliums 

Berichte,  n,  872. 

Chem.  Centrbl,  1878,  467. 

Jsb.  Chem.,  1878,  70. 

Chem.  News.,  38,  59. 

J.  Chem.  Soc.    (London),  34,  704. 

J.  Russ.  Phys.  and  Chem.  Soc.,  n,  II,  49. 
Discusses  N..  and  P.   (1878;  3),  work  on  specific  heat 
and  predicts  that  if  determined  at  higher  temperature 
and  density  of  BeCl2  be  found,  Be  will  be  found  to 
be  divalent. 

1878;  7.  Nilson,  L.  F.  Om  jodhaltiga  derivat  of  platonitrit, 
(Beryllium  platojodonitrite). 

Ofvsgt,  Akad.  For.  Stockholm,  35,  number  3,  51. 

Nova  Acta  Soc.  Sci.  Upsala,  10,  (1879),  number  16. 

Berichte,  u,  884. 
J.  prakt.  Chem.,  21,  172,  (complete). 


106  CHEMISTRY  OF   BERYUJUM 

Bull.  soc.  chim.,  (2),  31,  361. 

Chem.  News.,  38,  49. 

J.  Chem.  Soc.  (London),  34,  706. 

Chem.  CentrbL,  1880,  261. 

Jsb.  Chem.,  1878,  312. 

J.  Russ.  Chem.  Soc.,  n,  II,  305. 
Made  BePtI2(NO2)2+6H2O. 

1878;  8.  Nilson,  L.  F.  and  Pettersson,  Otto.  Ueber  das 
Atomgewicht  des  Berylliums,  (Erwidering  an  Lothar 
Meyer) . 

Berichte,  n,  906. 

J.  Russ.  Phys.  and  Chem.  Soc.,  n,  II,  49. 
Discussion  of  1876;  3  and  1878;  5. 
1878;  9.     Rossler,  C.     Ueber  die  Nachweisung  des  Berylliums. 

Ztschr.  anal.  Chem.,  17,  148. 

Chem.  CentrbL,  1878,  600. 

Jsb.  Chem.,  1878,  1059. 

Chem.  tech.  Rep.,  1878,  422. 

J.  Chem.  Soc.  (London),  34,  606. 

Bull.  soc.  chim.  (2),  32,  365. 

J.  Russ.  Phys.  and  Chem.  Soc.,  II,  83. 
By  adding  an  excess  of  ammonium  phosphate  to  a  beryl- 
lium salt,  dissolving  the  precipitate  in  HC1,  adding  NH4- 
OH  to  neutral  reaction,  avoiding  excess,  and  heating  to 
boiling,  precipitate  becomes  crystalline  and  settles 
quickly.  Na  phosphate  not  applicable.  Serves  to  separate 
from  small  amounts  of  Al  if  citric  acid  is  present. 
Larger  amounts  of  Al  must  first  be  removed  by  heating 
to  180°  n  sealed  tube  with  excess  of  saturated  solution 
of  K2SO4.  His  phosphate  was  analagous  to  the  similar 
magnesium  compound,  but  varied  somewhat  in  com- 
position so  he  did  not  assign  formula. 

1878;  10.  Lockyer,  V.  N.  Researches  in  spectrum  analysis 
in  connection  with  the  spectrum  of  the  sun. 

Proc.  Roy.  Soc.  (London),  27,  279. 
Includes   Be  in  table  of  elements  probably  present  in 

sun. 


BIBLIOGRAPHY  OF  BERYLLIUM  IO7 

1878;  ii.  Sorret,  J.  L.  Recherches  sur  1'  absorption  des  rayons 
ultra  violets. 

Arch  des  sci.  phys.  et  nat.  de  Geneve,  (2),  63,  108, 

1878  and  (3),  4,  290,  1880. 

Solutions  of  BeCl2  give  no  absorption  bands  but  partially 
absorb  the  ultra  violet  light,  the  absorption  increasing 
with  the  refrangability. 

Ultra  violet  light  from  an  induction  spark  gives  a  faint 
blue  fluorescence  to  a  solution  of  beryllium  chloride. 
1879;  I.     Carnalley,  T.  Influence  of  atomic  weight  on  physical 
properties   of   compounds.     (Melting   points   of   BeCl2 
and  BeBr2). 

Phil.  Mag.,   (5),,  8,  281. 

Chem.  News.,  39,  281. 

Chem.  Centrbl.,  1880,  339. 

Jsb.  Chem.,  1879,  l8- 

J.  Chem.  Soc.  (London),  37,  125. 

Obtained  melting  point  of  BeCl2  and  BeBr2,  between 
858-890°,  which  are  in  reality  several  hundred  degrees 
too  high. 

1879;  2.  Mendeleef,  D.  La  Loi  Periodique  de^  Elementes 
chimiques. 

Moniteur  scientifique,  39,  691. 

Chem.  News.,  40,  303. 
Place  of  beryllium  in  system. 

1880;  i.  Carnalley,  T.  and  Carleton,  Williams,  W.  The  melt- 
ing and  boiling  points  of  certain  inorganic  solvents. 

J.  Chem.  Soc.  (London),  37,  125. 

Apparently  again  determined  the  melting  points  of 
BeCl,  and  BeBr2  as  between  585-617°,  but  on  next 
page  repeats  his  old  figures  of  858-890°,  both  of  which 
are  much  too  high. 

1880;  2.  Vincent,  Camille.  Note  sur  les  reactions  produits 
par  la  di-methylamine  aqueuse  sur  les  dissolutions 
metalliques. 

Bull.  soc.  chim.,  33,  157. 

Chem.  Centrbl.,  1880,  278. 

Zcit.  anal.  Chem.,  17,  479. 


108  CHEMISTRY  OF   BERYLLIUM 

Dimethyl   amine  precipitates  beryllium   from   solutions 
of  its  salts  as  a  white  precipitate    insoluble    in    excess, 
(also  Fe,"  F/"  and  Zr).  Says  like  precipitate  from  Al 
salts  is  soluble  in  excess.     See  also  Renz,  1903. 
1880;  3.     Humpidge,  T.   S.     Atomic  weight  of  beryllium. 

Chem.  News.,  42,  261. 

Chem.  Centrbl.,  1881,  36. 

Jsb.  Chem.,  1880,  290. 

Berichte,  13,  2412. 

Agrees  with  Nilson  and  Petersson  that  Be  is  trivalent. 
1880;  4.     Reynolds,  J.  Emerson.     Atomic  weight  of  beryllium, 
note  on. 

Chem.  News.,  42,  273. 

Chem.  Centrbl.,  1881,  68. 

Jsb.  Chem.,  1880,  289. 

Berichte,  13,  2412. 

1880;  5.     Ciamician,  G.  L.     Uber  des  Spectrum  des  Berylliums 

Sitzber,  Akad.  Wein  (2),  82,  425. 

Monatshefte  fur  Chemie,  I,  662. 

Ztschr.  anal  Chem.,  20,  411. 

Spark  spectra  between  beryllium  electrodes  is  homol- 
ogous with  spectra  of  C.  B  and  Mg.  Obtained  only 
a  spectra  of  second  order,  a  three-fold  line  2  c :  509.7 ; 
508.8;  508.,  in  green  and  an  intense  violet  line  3  c, 
401.5. 

1880;  6.  Nilson,  L.  F.,  and  Pettersson,  Otto.  Om  beryl- 
liums atomwigt  och  vasendtliga  egenskaper  (atomic 
weight  and  essential  properties). 

Ofers.  af.  K.  Sven.  Vet.  Akad.  Forh.,  1880,  No.  6, 

page  33. 

Berichte,  13,  1451-59. 

Chem.  Centrbl.,  1880,  612. 

Jsb.  Chem.,   1880;  4,  238. 

Jour.  Chem.  Soc.   (London),  38,  850. 

Chem.  News,  45,  13. 

Jour.  Russ.  Phys.  and  Chem.  Soc.,  13,  II,  273. 

Ztschr.  anal.  Chem.,  21,  483. 


BIBLIOGRAPHY  OF  BERYUJUM  IO9 

Determined  atomic  weight  by  ignition  of  hydrous  sul- 
phate. Sulphate  made  from  sublimed  chloride  and 
crystallized  three  times  from  excess  of  H2SO4.  Dried 
between  blotting  paper. 

Made  metal  94  per  cent,  pure  and  determined  specific 
heat  at  300° =5056. 
Long  discussion  favoring  trivalency  of  beryllium. 

1880;  7.     Nilson,  L.  F.,  and  Pettersson,  Otto.     On  the  Essen- 
tial Properties  and  Chemical  Characters  of  Beryllium. 
Read  before  Royal  Soc.,  Nov.  18,  1880. 
Chem.   News,  42,  297. 
Berichte,  14,  259. 

J.  Chem.   Soc.    (London),  40,  511. 
Separate  presentation  of  1880;  6. 

1880;  8.  Nilson,  L.  F.  and  Pettersson,  Otto.  Sur  le  poids 
atomique  eat  les  proprietes  principales  da  glucinum. 

Comptes  rend.,  91,  168. 

J.  Chem.  Soc.  (London),  38,  792. 
Separate  report  to  French  Academy  of  1880;  6,  but  not 
so  complete  as  in  Berichte,   13,   1451. 

1880;  9.  Nilson,  L.  F.,  and  Pettersson,  Otto.  Om  de  sallsyn- 
ta  jordarternas  och  deras  sulfats  molkylarvarme  och- 
volym.  (The  molecular  heat  and  molecular  volume 
of  the  rare  earths  and  their  sulphates). 

Of.  af.  K.  Sv.  Akad.  Forh.,  1880,  No.  6,  p.  45. 

Berichte,  .13,    U59- 

Jsb.  Chem.,  1880,  291. 
Found  the  following  figures  based  on  trivalency  of  Be: 

Be2.  Molecular  weight,  75.3;  specific  gravity,  3.016;  specific  heat, 
2471;  molecular  heat,  18.61 

Be2(SO4)3.  Molecular  weight,  315.3;  specific  gravity,  2.443;  spe- 
cific heat,  0.1978. 

Be,(SO4)3+i2H2O.      Molecular  weight,   531.3;  specific  gravity, 
I.7I3 
Be2O3   diamagnetic. 


110  CHEMISTRY  OF   BERYLLIUM 

^ 

1880;  10.  Nilson,  L.  F.,  and  Pettersson,  Otto.  Sur  les  chal- 
eur  et  le  volume  moleculaires  des  terres  rare  et  de 
leur  sulfates. 

Comptes  rend.,  91,  232. 
Separate  report  to  the  French  Academy  of   1880;  9. 

1880;  ii.  Meyer,  Lothar.  Ueber  das  Atomgewicht  des  Beryl- 
lium. 

Berichte,  13,  1780. 

Bull.   soc.  chim..    (2)    36,   152. 

Chem.  Centrbl.,  1880,   1789. 

Arch,  der  Pharm.,  218,  68.  » 

Chem.  Ztg.,  4,   752. 

Chem.   News,  46,  159. 

J.  Russ.  Phys.  and  Chem.  Soc.,  13,  II,  273. 

J.  Chem.   Soc.    (London),  40,   139. 

Amer.  Chem.  J.,  2,  360. 

Discussion   of   results    of   Nilson    and    Pettersson    and 
others  and  comes  to  the  conclusion  that  Be  is  divalent. 

1880;  12.  Nilson,  L.  F.  Zur  Frage  nach  dem  Atomgewicht 
des  Berylliums. 

Berichte,   13,  2035. 

J.   Chem.   Soc.    (London),   40,    140. 

Chem.  Centrbl.,  1881,  36. 

Amer.  Chem.  J.,  2,  433. 
Reply  to  1880;  ii. 

1881 ;  i.  Brauner,  Bohuslav.  Ueber  das  Atomgewichte  des 
Berylliums. 

Berichte,  14,  53. 

Chem.   Centrbl..   1881,  298. 

Jsb.  Chem.,  1881,  4. 

Phil.   Mag.,    (5)    ii,   65. 

J.  Chem.  Soc.,  40,  224. 

Chem.  Ztg.,  5,  79- 

J.  Russ.  Phys.  and  Chem.  Soc.,  14,  II,  63. 
Excellent  discussion  of  the  probable  valency  of  Beryl- 
lium and  favors  divalency. 


BIBLIOGRAPHY  OF  BERYLLIUM  III 

1 88 1 ;  2.  Reinsch,  H.  Ueber  die  Erkennung  und  Untersch- 
heidung  der  Kiesel-Thon,  und  Beryllerde,  der  Borsaure 
der  Alkalien  und  einiger  Metalle  durch  das  Mikroskop. 

Berichte,   14,  2325. 

Chem.   Cenrbl.,    1882,   56. 

Jsb.  Chem.,  1881,   1183. 

Bull.  soc.  chim.,  (2)  37,  525. 

Chemisches    Ind.,  4,  428. 

Arch.  der.  pharm.,  220,  68. 

Says  that  the  sulphate  forms  very  characteristic  crys- 
tals under  the  microscope  which  enables  it  to  be  iden- 
tified at  once. 

1 88 1 ;  3.  Classen,  Alex.  Elektrolytische  Bestimmung  und 
Trennung. 

Berichte,   14,  2782. 

Chem.  Centrbl.,   1882,  233. 

Jsb.  Chem.,   1882,   1152. 

Ding.  Poly.  J.,  242,  440. 

Bull.  soc.  chim.,  (2)  37,  526. 

Ztschr.  anal.  Chem.,  22,  440. 

Separates  Fe  and  Al  from  Be  by  electrolysis  in  ammo- 
nium oxalate  solution.  Iron  reduced.  Aluminum  pre- 
cipitated by  use  of  stronger  current,  as  hydroxide  by 
ammonium  carbonate  produced  and  beryllium  left  in 
solution. 

1 88 1 ;  4.  Crookes,  W.  On  Discontinuous  Phosphorescent 
Spectra  in  High  Vacuo. 

Proc.  Roy.  Soc.,  32,  206. 

Chem.  News,  43,  237. 

Annales  chim.  et  phys.,   (5)   23,  555   (complete). 

Comptes  rend.,  92,  1281. 

Jsb.  Chem.,  1881,  130. 

Carefully  prepared  BeO  gave  a  fluorescence  of  a  beau- 
tiful blue,  but  no  spectral  rays.  Under  conditions  giv- 
en it  shows  only  a  concentration  of  light  in  the  blue. 


112  CHEMISTRY   OF   BERYLUUM 

1882;   i.     Blake,   James.     Atomic   weight   of  beryllium   as  de- 
termined by  its  physiological  actions. 

Chem.  News,  45,  HI. 

Jsb.  Chem.,  1882,  15. 

J.  Chem.  Soc.   (London),  42,  701. 
Found  that  physiological  action  of  sulphate  injected  in- 
to the  blood  was  analogous  to  members  of  aluminum 
family,   from  which    he    concludes    that    beryllium    is 
trivalent. 

1882;  2.     v.  Bemmelen,  J.  M.     Die  Hydrate  des  Btrylloxyds. 
J.    prakt.    Chem.,    (2)    26,   227-246. 
Bull.  soc.  chim.,  (2)  39,  514. 
Chem.   Centrbl.,   1883,  36. 
Jsb.   Chem.,   1882,  275. 
Berichte,    15,    2902. 
Chem.   News,  46,  291. 
J.  Chem.  Soc.   (London),  44,  291. 
Rec.  trav.  chim.  de  Pays  Bas.,  I,  271. 
J.  Russ.  Phys.  and  Chem.  Soc.,  15,  II,  453. 

A  long  study  of  the  hydroxides  of  beryllium.  Dis- 
tinguishes two  hydroxides,  1st.  Alpha,  made  by  boiling 
KOH  solution,  and  2nd.  Beta,  made  by  precipitating 
salts  with  ammonia.  Only  the  first  has  definite  com- 
position. 

1882;  3.     de  Boisbaudran,  Lecoq.      Separation  du  gallium. 
Comptes  rend.,  94,  1439. 
Jsb.  Chem.,  1882,   1295. 

Separated  from  beryllium  by  precipitating  gallium  by 
potassium  ferrocyanide  in  acid  solution. 

1883;    i.     Wallroth,   K.   A.     Action   du   sel   de  phosphore  sur 
divers  oxydes. 

Bull.  soc.  chim.,  39,  316. 

Chem.   Centrbl.,  1883,  290. 

Obtained  BeNaPO4  by  fusing  BeO  in  sodium  meta- 
phosphate.  Insoluble  hexagonal  plates. 


BIBLIOGRAPHY  OF  BERYUJUM  113 

1883;  2.     Philipp,  Jul.     Ueber  basisches  Beryllium-Kalium  Ox- 
alate. 

Berichte,  16,  752. 

Jsb.   Chem.,    1883,    1045. 

Bull.  soc.  chim.,  (2)  40,  373. 

Mentions  Debray's  BeC2O4.3K3C2O4  and  Be(C2O4). 
3(NH4)2C2O4  and  states  that  last  salt  is  characteristic 
in  its  crystallization  for  beryllium  and  is  valuable  in 
purification.  Made  a  new  salt  to  which  he  gave  the 
trivalent  formula  Be2(C2O4)3.3K2C2O4.Be2(OH)6  + 
5H2O,  by  saturating  acid  potassium  oxalate  with 
Be  (OH)  2,  evaporating  and  cooling  in  desiccator. 
J883;  3.  Donath,  Ed.  and  Mayrhofer,  J.  Bemerkungen  iiber 
Affinitat  und  deren  Beziehungen  zu  Atomvolum,  At- 
omgewicht  und  specific  Gewicht. 

Berichte,    16,    1590. 

Jsb.  Chem.,  1883,  26. 

Uses  determinations  of  others  on  beryllium  in  his  dis- 
cussion. 

1883 ;  4.     Clarke,  F.  W.  A  recalculation  of  the  Atomic  Weights. 
(Glucinium). 

Chem.  News,  48,  289.     (From  Constants  of  Nature). 

Chem.  Ztg.,  8,  21. 

A  recalculation  of  all  determinations  of  atomic  weight 
of  beryllium  up  to  1883  and  discussion  of  same. 
1883;  5.     Hartly,  W.  N.     On  the  Spectrum  of  Beryllium  with 
observations  relative  to  the  position  of  the  metal  among 
the  elements. 

J.  Chem.   Soc.    (London),  43,  316. 

Chem.   Centrbl.,   1883,  380. 

Jsb.  Chem.,   1883,  246. 

Bull.  soc.  chim.,  (2)  41,  642. 

Chem.  News,  47,  201. 

J.  Amer.  Chem.   Soc.,  5,   115. 

J.  Russ.  Phys.  and  Chem.  Soc.,  16,  II,  63. 
Studies  spectrum  of  beryllium  and  concludes  that  con- 
clusion of  Nilson  and  Pettersson  is  wrong  as  to  tri- 
8 


114  CHEMISTRY   OF 

valency  of  beryllium  and  claims  that  its  spectra  shows 
it  to  be  the  first  member  of  a  dyad  series  of  which,  in 
all  probability,  Ca,  Ba,  and  Sr  are  homologues.     Ar- 
ticle contains  fine  chart  of  spectra  of  beryllium. 
1883 ;  6.     Haushofer,  K.     Beitrage  zur  mikroskopischen  Analyse 

Sitzungsberichte    'd.    Kon.    Bayr.    Akad.    der   Wiss., 

1883,  p.  436;  1884,  p.  690. 

Ztschr.  fur  Kryst,   n,   166;,  13,   173. 

Berichte,  18,  238. 

Jsb.  Chem.,  1885,   1880. 

Recommends  beryllium  platinum  chloride,  which  is 
easily  soluble  in  water  as  microscopic  test  for  Be.  Made 
by  action  of  PtCl4  on  beryllium  salt  and  evaporation 
in  desiccator.  Tetragonal  crystals. 

1883;  7.     Humpidge,  T.   S.     On  the  Atomic   Weight  of  Glu- 
cinum. 

Chem.  News,  47,   181. 

Froc.    Roy.    Soc.    (London),   35,    137. 

Trans.   Roy.    Soc.    (London),    174,    601. 

Chem.  Centrbl.,  1883,  380. 

Jsb.  Chem.,  1883,  35. 

Chem.  Ztg.,  7,  648. 

Berichte,  16,  2494. 

Determined  specific  heat  as  4453  from  a  94  per  cent, 
metal  made  by  action  of  Na  on  BeCl2.  Speaks  of  the 
possibility  of  electrolyzing  double  fluoride  of  K  and 
Be,  but  says  material  is  very  impure  from  fluorine  at- 
tacking containing  vessel.  Gives  many  properties  of 
Be  and  BeO  not  consistent  with  those  of  later  inves- 
tigators. Main  study  was  evidently  on  specific  heat, 
which  being  obtained  at  low  temperatures,  lead  him  to 
the  belief  in  trivalent  beryllium. 

1883;  8.     Reynolds,   J.   Emerson.     Atomic   Weight  of   Berylli- 
um, Note  on. 

Chem.   News,  47,  251. 

Proc.  Roy.  Soc.  (Lon.),  35,  248. 

Chem,  Centrbl.,  1883,  471. 


BIBLIOGRAPHY  OF  BERYUJUM  115 

Jsb.  Chem.,  1883,  36. 

Jour.  Chem.  Soc.   (Lon.),  46,  261. 

Berichte,  16,  2494. 

1883;  9.  Humpidge,  T.  S.  Reply  to  a  note  by  J.  E.  Reynolds 
on  the  Atomic  Weight  of  Glucinum  or  Beryllium. 

Chem.  News,  47,  297. 

Proc.  Roy.  Soc.  (Lon.),  35,  358. 

Chem.  Centrbl.,  1883,  501. 

Jsb.  Chem.,  1883,  35- 

Chem.  Ztg.,  7,  873. 

Berichte,  16,  2659. 

1883;  10.  Reynolds,  J.  Emerson.  Note  in  Regard  to  Hum- 
pidge's  "Reply"  on  Beryllium. 

Chem.  News,  48,  9. 

1884;  i-  Penfield,  Sam'l  L.  On  the  occurrence  of  alkalies  in 
Beryl. 

Amer.  J.  of  Sci.,   (3)   28,  25. 

Found  Na,  Li  and  H2O  present,  also  Cs  in  two  samples. 
Gives  method  of  analysis  used. 

1884;  2.  Lavroff,  V.  L'action  du  beryllium  metalique  sur  le 
mercure-dimethyle,  (Preliminary  announcement  of 
1884;  3). 

Bull.  soc.  chim.,   (2)   41,  548. 
1884;  3.     Lavroff,  V.     Beryllium  Methyl. 

J.  Russ.  Phys.  and  Chem.  Soc..  16,  93. 
By  the  action  of  metallic  beryllium  on  mercury  methyl 
in  sealed  tubes  at  130°,  he  obtained  a  white  volatile 
crystalline  substance,   decomposed  by  water  with  evo- 
lution  of   light   into    methane    and   Be(OH)2. 
1884;  4-     Brogger,  W.   C.,  and  Flink,  Gust.     Ueber  Krystalle 
von  Beryllium  und  Vanadium. 

Ztschr.  fur  Kryst,  9,  228-236. 

Berichte,  17,  849. 

Chem.  Ztg.,  8,  670. 

Bui.  de  la  soc.  franc,  d.  min.,  7,  412. 

Bull.  soc.  chim.,  (2)  43,  561. 

J.  Chem.  Soc.  (Lon.),  46,  1092. 


Il6  CHEMISTRY  OF   BERYLLIUM 

Used  the  beryllium  crystals  made  by  Nilson  and  Pet- 
tersson  by  action  of  Na  on  BeCl2. 
System  Hexagonal  and  holohedral. 

Type  I.     Prismatic  crystals. 

ooP  :  ooP'  ==59°,  59^', 
oo p'  :  oo P"  =  60°,  n#', 
ooP  :  oP  =89°,  55^'. 

Type  II.     Tabular  crystals. 

P   :      P    =  57°,  3i', 

P'  :      F     =  56°,  20',  (poor) 

P   :  ooP      =  28°,  n'. 

Axis  relation 
a:c=i : i. 5802. 

Also  examined  crystals  made  by  T.  S.  Humpidge  and 
found  them  to  belong  to  the  holohedric  division  of  Hex- 
agonal System. 

1884;  5.     Hartley,  W.  N.     The  Atomic  Weight  of  Beryllium, 
Remarks  on. 

Proc.  Roy.  Soc.   (Lon.),  36,  462. 

Chem.  News,  49,   171. 

Jsb.  Chem.,  1884,  49. 

J.  Chem.  Soc.   (Lon.),  48,  484     . 

Discussion  of  his  previous  work  on  Spectra  of  Beryllium 
and  its  position  among  the  elements. 
1884;  6.     Genth,  F.  A.     On  Herderite. 

Proc.  Amer.  Phil.  Soc.,  21,  694. 

Chem.  News,  51,  86. 

Points  out  that  BeO  is  slightly  soluble  in  a  boiling  solu- 
tion of  NH4C1,  and  discusses  methods  of  determining 
BeO. 

1884;   7.     Nilson,    L.    F.,    and    Pettersson,   Otto.        Ueber   die 
Dampfdichte  des  Chlorberylliums. 

Berichte,  17,  987. 

Jsb.  Chem.,  1884,  61. 

Chem.  Ztg.,  8,  669. 

Bull.  soc.  chim.,  44,  32. 


BIBLIOGRAPHY  OF  BgRYLUUM  117 

Amer.  J.  ScL,  (3)  28,  149. 

Tidskrift,  23,  310. 

Arch.  der.  Pharm.,  222,  462. 

Amer.  Chem.  J.,  6,  215. 

Found  the  density  of  BeCl2  at  different  points  between 
490°  and  812°,  overthrew  all  their  previous  ideas  of  the 
subject  and  proved  the  divalency  of  beryllium.  Full 
details  of  preparation,  apparatus  and  method  used. 
1884;  8.  Nilson,  L.  F.  and  Pettersson,  Otto.  Determinations 
de  la  densite  des  vapeurs  du  chlorur  de  glucinium. 

Comptes  rend.,  98,  988. 

Chem.  News,  49,  255. 

J.  Chem.  Soc.   (Lon.),  46,  820. 

Chem.  Centrbl.,  1884,  452. 

Separately  transmitted  to  French  academy.  Same  as 
1884,  7.  " 

1884;  9-  Carnalley,  T.  Applications  of  Melting  and  Boiling 
points  to  the  classification  of  the  Atomic  Weights  of 
Elements. 

Phil.  Mag.  (5),  18,  21. 

Uses  same  result  of  previous  work,  (1879;  i)  in  dis- 
cussion. 

1884;  10.  Carnalley,  T.  Ueber  die  Schmelzpunkte  von  Chlor 
und  Bromberyllium. 

Berichte,  17,  1357. 

J.  Chem.  Soc.  (Lon.),  46,  962. 

Repeats  with  careful  precaution  his  earlier  work  and 
defends  his  previous  results  (1879;  *)»  which  are  much 
too  high. 

1885  ;  i.     Humpidge,  T.  S.  On  the  Atomic  Weight  of  Glucinium. 
Proc.  Roy.  Soc.  (Lon.),  38,  188. 
Chem.  News,  51,  121. 
Jsb.  Chem.,  1885,  32. 
J.  Am.  Chem.  Soc.,  7,  113. 
J.  Chem.  Soc.  (Lon.),  48,  1184. 
Berichte,  18,  258. 
Advance  report  of  1886;  i. 


Il8  CHEMISTRY  OF   BERYUJUM 

1885;  2.  Tammann,  G.  Ueber  die  Dampftensionen  von  Salz- 
losungen. 

Ann.  der.  Phys.   (Wied.),  24,  554. 
Mem.  de  1'academy  imp.  de  St.    Pets'bg.    35,    No.    9, 
1887. 

Ztschr.  phys.  Chem.,  2,  45. 

Jsb.  Chem,  1888,  185. 

Gives  figures  on  the  lowering  of  the  vapor  tension  by 
beryllium  sulphate  in  comparison  with  other  sulphates. 
Shows  its  molecular  weight  to  be  represented  by 
BeSO44H2O.  Gives  results  also  for  chloride,  brom- 
ide and  nitrate. 

1885;  3.  Nilson,  L.  F.  and  Pettersson,  Otto.  Ueber  ein 
Neues  mit  exacter  Temperature  Bestimmung  verbun- 
denes  Verfahren  zur  Feststellung  der  Dampfdichte 
fliichtiger  Korper.  Read  at  Kon.  Ak.  der.  Wiss. 
Stockholm,  Sept.  16,  1885. 

Jr.  prakt.  Chem.  (2),  33,  1-17,  (complete). 

Ann.  de  chim.  et  de  phys.   (6),  9,  554,  (complete). 

Chem.  Centrbl,  1886,  130. 

Jsb.  Chem.,  1886,  59. 

J.  Russ.  Chem.  and  Phys.  Soc.,  18,  II,  92. 
Prepared  BeCl2  in  platinum  by  action  of  dry  HC1  on 
Be  and  redetermined  density  between  490°   and  1520° 
C.     Obtained    quite    closely    agreeing     results     above 
1000°.     Interesting  description  of  apparatus     used     to 
prevent  the  chloride  coming  in  contact  with  water  or 
glass.     Decided  addition  to  previous  work. 
1886;  i.     Humpidge,  T.  S.     Atomic  weight  of  beryllium. 

Proc.  Roy.  Soc.  (Lon.),  39,  i. 

Jsb.  Chem.,  1886,  44. 

J.  Chem.  Soc.  (Lon.),  50,  506. 

Berichte,  19,  202. 

J.  Russ.  Phys.  and  Chem.  Soc,  18,  II,  in. 
Determined  specific  heat  of  Be  on  a  specimen  99.2  per 
cent,  pure  at  temperatures  up     to     450°.     The     curve 
representing  relation  between  specific  heat  and  tempera- 


BIBLIOGRAPHY  OF  BERYUJUM  119 

ture  reaches  a  maximum  at  400°  and  remains  practically 
constant  between  400°  and  500°.  Figures  obtained  places 
Be  with  C.  B.  and  Si,  as  accordant  with  law  of  Du- 
long  and  Petit  at  high  temperature.  Also  determine 
density  of  BeCl2  and  BeBr2. 

Also  made  a  double  carbonate  of  evidently  indefinite 
composition  to  which  he  gives  the  formula:  2(BeCO3.- 
(NH4)2CO3)  Be(OH)2+2H2O. 

1886;  2.     Grandeau,   H.     De  1'action  du   sulfate   de  potasse   a 
temperature  elevee  sur  les  phosphates  metalliques. 

Ann.  de  chim.  et  de  phys.  (6),  8,  212. 

Jsb.  Chem.,  1886,  358. 

Made  K2Be2(PO4)2  by  fusing  the  sulphate  and  phos- 
phates together.     Specific  gravity  BeO=3.i8. 
1886;  3.     Strohecker,   R.     Berylloxyd   in   diluvialen   Thonen. 

J.  prakt.  Chem.,  (2)  33,  132. 

Jsb.  Chem.,  1886,  407. 

Chem.  News,  53,  136;  54,  207. 

1886;  4.     Penfield,  S.  L.  and  Harper,  D.  N.  Chemical  composi- 
tion of  Herderite  and  Beryl. 

Am.  J.  Sci.,  (3)  32,  107. 

Chem.  News,  54,  90. 

Berichte,  19,  797. 

Chem.  Industrie,  10,  366. 

Analysis  and  discussion  of  methods  of  separation  of 
beryllium  from  aluminum. 

1886;  5.     Chabrie,  C.     Note  preliminaire    sur    les    fluosilicates 
d'aluminium  et  de  glucinium. 

Bull.  soc.  chim.,  (2)  46,  284. 

Chem.  Centrbl.,  1886,  771. 

Jsb.  Chem.,  1886,  399. 

J.  Chem.  Soc.,  50,  981. 

Berichte,  19,  871. 

1886;  6.     Cooke,  J.   P.     On  Danalite,  a  new  Mineral   Species 
from  the  Granite  of  Rockland,  Mass. 

Amer.  J.  Sci.  (2),  42,  78. 

Ztschr.  and  Chem.  6,  226. 


120  CHEMISTRY  OF   BERYLLIUM 

Gives  method  of  analysis  and  separated  iron  from 
beryllium  by  reducing  the  former  in  a  current  of  hy- 
drogen and  volatilizing  it  in  a  current  of  hydrochloric 
acid  gas. 

1887;  J-     Meyer,    Lothar.     Ueber    die    Einwirkung   von    Chlor 
kolenstoff  auf  Oxyde. 

Berichte,  20,  68 1. 

Jsb.  Chem.,  1887,  379- 

Found  he  could  make  many  metallic  chlorides  by  pass- 
ing CC14  over  oxides  when  heated,  among  them  BeCl2. 
1887;  2-     Ebel,   Fr.     Ueber  antimonsaure   Salze. 

Berichte,  22,  3044. 

J.  Chem.  Soc.  (Lon.),  58,  216. 

Made  BeSb2O6.6H2O  by  dissolving  Na2H2Sb2O7.7H2O 
in  boiling  water  and  adding  a  soluble  beryllium  salt. 
1887;  3-     Crookes,     W.     Radiant    Matter    Spectroscopy.     Ex- 
amination of  the  residual  glow. 

Proc.  Roy  Soc.,  42,  in. 

J.  Chem.  Soc.  (Lon.),  52,  1066. 

Examined  BeO  among  other  oxides.  Found  it  to  give 
a  rich  blue,  but  no  residual  glow. 

1887 ;  4.     Mallard,  E.     Sur  quelques  substances  cristallisees  pre- 
parees  par  Ebelmen. 

Bui.  de  la  soc  franc,  de  min.,  n,  305. 

Ztschr.  f.  Kryst.,  14,  605;  15,  650. 

Ann.  d.  mines,  12,  427,  460. 

Comptes  rend.,  105,  1260. 

Jsb.  Chem.,  1887,  384. 

J.  Chem.  Soc.   (Lon.),  54,  349. 

By  fusing  chromic  oxide  and  BeO  in  presence  of  boric 
anhydride  and  calcium  carbonate  Ebelmen  obtained 
a  product  which,  after  treatment  with  hydrochloric 
acid,  left  a  crystalline  chromite  analagous  to  Alex- 
andrite. 

From  crystals  of  BeO  prepared  by  Ebelmen,  he  obtain- 
ed parameters  a  :  h  =  I ;  1.6305,  isomorphous  with 
ZnO,  positive  and  uniaxial.  Made  artificial  phenacite 


BIBLIOGRAPHY  OF  BERYLLIUM  121 

Be2SiO4  by  fusing  silica,  beryllia  and  borax  together 
in  optically  positive  hexagonal  prisms. 

1887 ;  5.  Zimmermann,  A.  Ueber  die  Trennung  der  Thonerde 
und  Beryllerde. 

Inaugural  Dissertation,  Berlin,  1887. 

Ztschr.  f.  anorg.  Chem.,  15,  285. 

Ztschr.  f.  anal.  Chem.,  27,  61. 

Chem.  News,  58,  49. 

J.  Chem.  Soc.    (Lon.),  54,  323. 

Separated  by  boiling  a  solution  in  KOH.  Also  recom- 
mends separation  by  boiling  with  sodium  thiosulphate 
after  neutralization  with  Na2CO3.  Not  new  and 
separations  far  from  perfect. 

1888;  i.  Neumann,  G.  Ueber  Doppelsalze  von  Sesquichloriden 
mit  anderen  Metallchloriden. 

Ann.  der  Chem.    (Liebig.),  244,  335. 

Chem.  Centrbl.,  1888,  709. 

Made  BeCl2.FeCl3  +  H2O  and  BeCl2.CrCl3  +  H2O 
3BeCl2.Tl2Cl6. 

1888;  2.  Kluss,  K.  Zur  Kentniss  der  Unterschwefelsauren 
Salze.  Unterschwefelsaures  Beryllium. 

Ann.  der  Chem.   (Liebig.),  246,  195. 

Bull.  soc.  chim.,  (3)  2,  14. 

5BeO.2S2O3-|-i4H2O.  Basic  salt,  colorless  gummy  mass. 
Loses  H2O  and  SO2  on  heating.  Made  by  carefully 
evaporating  a  solution  of  Be(OH)2  in  dithionic  acid. 
(Probably  an  indefinite  solid  solution). 

1888;  3.  Sestine,  F.  Ueber  einige  selten  in  Planzen  vorkom- 
mende  und  seither  noch  nicht  darin  gefundene  chemis- 
che  Elemente,  Spezielle  iiber  Beryllium  mit  Riicksicht 
auf  einige  Kultwerke  Planzen. 

Chem.   Centrbl.,   1888,   1622.     From. 

Staz.  Sperim.  Agrar.,  15,  290-298. 

Jsb.  Chem.,  1888,  2556. 

Found  beryllium  in  ash  of  plants  which  had  been  fed 
with  BeSO4,  instead  of  MgSO4.  Also  in  plants  from 
beryllium  containing  soils. 


122  CHEMISTRY  OF   BERYLUUM 

1888;  4.     Hautefeuille,  P.  and  Perrey,  A.     Sur  1'action  mineral- 
istetrice  des  sulfures  alcalins. 
Comptes  rend.,  106,  487,  1800. 
Jsb.  Chem.,  1888,  555,  557,  558. 
Chem.  News,  58,  24. 
Ztschr.  f.  Kryst,  18,  322. 
Berichte,  21,  175,  599. 
Prepared  artificial  phenacite  and  emerald. 

1888;  5.     Hautefeuille,  P.  and  Perrey,  A.     Sur  les  combinasions 
silicates  de  la  glucine. 
Comptes  rend.,  107,  786. 
Chem.  CentrbL,  1888,  1569. 
Ztschr.  f.  Kryst.,  18,  328. 
J.  Chem.  Soc.,  56,  104. 
Berichte,  21,  887. 

If  constituents  of  a  beryllium  leucite  are  fused  at 
6oo°-8oo°  in  excess  of  potassium  vanadate,  crystals 
are  obtained  of  heterogeneous  composition  and  which 
he  concludes  may  be  considered  as  mixtures  of  the  fol- 
lowing : 

2K2O.Be2Os-8SiO2, 
K2O.Be2Ov4Si02, 
2K2O.Be263.ioSiO2, 
K2O.Be203.5Si02. 

Claims  Be  can  replace  Al  in  above  and  also  in  ortho 
clase. 

1889;  i.     Stolba,  Fr.     Aufschliessung  des  Berylls  mit  Atzlauge 
Listy  chemicke,  (Prag.),  13,  117. 
Chem.  Centrbl.,  1889,  I,  297. 

Claimed  to  act  upon  finely  divided  beryl  with  10  per 
cent.  NaOH  solution  so  that  it  was  decomposed  by 
HC1. 

2.     Dana,     E.     S.     and     Wells,  H.     L.       New  Mineral, 
Beryllonite. 

Am.  J.  Sci.,  (3)  37,  23-32. 
Chem.  Centrbl.,  1889,  I,  141 ;  1890,  I,  337. 
Ztschr.  f.  Kryst.,  17,  592. 
Gives  method  of  analysis  in  brief. 


BIBLIOGRAPHY  OF  BERYLLIUM  123 

1889;  3-  Mendeleeff.  The  Periodic  Law  of  the  Chemical  Ele- 
ments (Faraday  Lecture,  June  '4,  1889). 

J.  Chem.  Soc.,  55,  650. 

Discussion  of  the  place  of  beryllium  among  the  ele- 
ments and  the  interesting  controversy  finally  settled  in 
favor  of  the  periodic  law. 

1889;  4.  Wulff,  G.  Optische  Studien  an  pseudosymmetrischen 
Krystallen.  Das  Beryllium  Sulfat. 

Ztschr.  f.  Kryst.,  17,  592. 

Cnem.  Centrbl.,  1890,  II,  73. 

Beryllium  sulphate  is  strongly  double  refractive,  is 
negative  and  uniaxial. 

1890;  i.  Moraht,  Hermann.  Untersuchungen  iiber  das  Beryllium. 
Inaugural  Dissertation,  Munich,  1890.  See  1890;  5 
and  1890;  7. 

1890;  2.  Sestini,  Fausto.  Proprieta  di  aleuni  sali  di  berillio 
e  die  corrispondenti  composti  di  alluminio. 

Gazzetta  chim.  ital.,  20,  313. 

Chem.  Centrbl.,  1890  II,  542. 

J.  Chem.  Soc.  (Lon.),  60,  151. 

Berichte,  23,  482. 

J.  Russ.  Phys.  and  Chem.  Soc.,  22,  II,  131. 
Rather  general  work  upon  the  phosphate  and  carbonate. 
Obtained  a  precipitate  to  which  he  gave  the  formula: 
3BeO.P2O5.3H2O+Ag.  Compared  the  solubility  of 
Be  (OH)  2  and  A1(OH)3  in  carbonated  waters.  Slight- 
ly greater  solubility  of  Be(OH)2  in  carbonate  water. 
1890;  3.  Winkler,  Clemens.  Ueber  die  Reduction  von  Sauer- 
stoffverbindungen  durch  Magnesium. 

Berichte,  23,  120. 

J.  Chem.  Soc.  (Lon.),  58,  451. 

Reduced  (only  partially)  BeO  by  Mg.  Reduction 
very  doubtful. 

1890;  4.  Kruss,  Gerhard  and  Moraht,  Hermann.  Unter- 
suchungen iiber  das  Beryllium. 

Berichte,  23,  727. 

Preliminary  communication  to  German  Chemical 
Society.  For  complete  details  see  1890;  5. 


124  CHEMISTRY  OF 

1890;  5.     Kruss,  Gerhard  and  Moraht,  Hermann.     Untersuch- 
ung  iiber  das  Beryllium  I. 

Ann.  der  Chem.,  260,   161. 

Chem.  CentrbL,  1890,  I,  794,  II,  734,  989. 

Jsb.  Chem.,  1890,  538. 

Bull.  soc.  chim.,   (3)  4,  377,  833. 

Chem.  News,  65,  12. 

J.  Chem.  Soc.  (Lon.),  58,  697. 

J.  Amer.  Chem.  Soc.,  12,  154. 

Ztschr.  anal.  Chem.,  31,  693. 

J.  Russ,  Phys.  and  Chem.  Soc.,  22,  II,  130. 
Prepared  impure  Be  in  hexagonal  plates  by  reduction 
of  K2BeFl4  with  sodium. 

Made  Be(OK)2  impure  which  was  easily  decomposed 
by  C02. 

Made  BeSO3  (in  absolute  alcohol)  and  gave  the 
formulas  BeO.BeSO3  and  BeO.3BeSO5  to  some  basic 
substances  obtained. 

Made  5BeO.B2O3  (dried  at  110°).     Research  was  car- 
ried on  to  show  the  weak  basic  character  of  Be. 
1890;  6.     Kruss,  Gerhard  and  Moraht,  Hermann.     Untersuch- 
ungen  iiber  das  Beryllium. 

Berichte,  23,  2552. 
Advance  communication  of  1890;  7. 

1890;  7.     Kruss,  Gerhard  and  Moraht,  Hermann.     Untersuch- 
ung  iiber  das  Beryllium,  II. 

Ann.  der  Ohem..  262,  38-61. 

Chem.  Centrbl.,  I,  569. 

Jsb.  Chem.,  1891,  491. 

Bull.  soc.  chim.,   (3)   8,  51. 

Ztschr.  phys.  Chem.,  7,  226. 

Chem.  News,  67,  242. 

J.  Chem.  Soc.,  (Lon.),  58,  697;  60,  881. 

J.  Amer.  Chem.  Soc.,  12,  154. 

Ztschr.  Anal.  Chem.,  30,  530. 

J.  Russ.  Phys.  and  Chem.  Soc.,  22,  II,  132. 
Prepared  BeSO44H2O  with  great  care  and  of  a  high    de- 


BIBLIOGRAPHY  OF  BERYLUUM  125 

gree  of  purity.  Material  from  several  sources.  Deter- 
mined the  atomic  weight  by  ignition  of  sulphate  after 
drying  over  phosphorus  pentoxide.  Mean  of  fourteen 
determinations  using  large  quantities  of  material  gave 
9.027  (O=i6).  Specific  gravity  of  BeSO44H2O  found 
to  be  17125.  Specific  gravity  660=2.9644. 
1.7125.  Specific  gravity  660=2.9644. 

1890;  8.     Petersen,  Emil.     Neutralizationsphanomene  des  Alu- 
minium und  Beryllium  Fluorid. 

Ztschr.  phys.  Chem.,  5,  259-266. 

Chem.  Centrbl,  1890,  I,  892. 

Berichte,  23,  270. 

J.  Chem.  Soc.  (London),  58,  680. 
Heat  of  neutralization  of  Be(OH)2+2HF.Aq=i9683 
calories. 

1890;  9.     Haute feuille,  P,  and  Perrey,  A.  Sur  la  cristallization  de 
1'alumine  et  de  la  glucine. 

Bull,  de  la  soc.  franc,  de  min.,  13,  149. 

Ztschr.   f.   Kryst,  21,  306. 

J.  Russ.  Phys.  and  Chem.  Soc.,  22,  II,  133. 

Chem.  Centrbl.,  1890,  II,  716. 

Prepared  crystals  of  beryllium  oxide,  by  dissolving  the 
oxide  in  fused  leucite.     Also  prepared  chrysoberyl. 
1890;  10.     Hautefeuille,    P.    and    Perrey,    A.     Sur    les  silico 
glucinates  de  soude. 

Comptes  rend.,  no,  344. 

Jsb.  Chem.,  1890,  143. 

Chem.  Centrbl.,  1890,  I,  668,  II,  716. 

J.  Chem.  Soc.  (London),  58,  562. 

Berichte,  23,  288. 

On  fusing  a  mixture  of  BeO,  SiO2  and  Na2O  (in  same 
proportion  as  in  a  beryllium  nephylene)  in  excess  of 
sodium  vanadate  at  about  800° C,  crystals  to  which 
they  gave  the  following  formula,  Na,O,  Be2O,,  3SiO2 
were  obtained.  Also  obtained  substances  to  which  they 
assigned  the  following  formulas: 
Na2O,  Be2O3.6SiO2, 


126  CHEMISTRY  OF   BERYLUUM 

2Na2O,  3Be2Os.  (20.67-22.41)  SiO2, 

3Na2O,2Be26s.i5SiO2, 

3Na2O,  2Be:iO3.i8SiO2, 

3Na2O, 


1890;  ii.  Ouvrard,  L.  Sur  quelques  phosphates  de  lithine,  de 
glucine,  de  plomb  et  d'urane. 

Comptes  rend.,    no,    1333-36. 

Chem.  Centrbl.,  1890,  II,  203. 

Chem.  News.,  62,  25. 

Bull.  soc.  chim.,  (3)  5,  80. 

J.  Chem.  Soc.  (London),  58,  1055. 

Berichte,  23,  550. 

By  fusing  with  potassium,  meta,  pyro  and  orthophos- 
phate,  obtained  K2O.2BeO.P2O5  in  rhombic  prisms. 
With  sodium  meta  and  pyrophosphate,  obtained  Na^O.- 
2BeO.P2O5,  in  hexagonal  plates  identical  with  beryl- 
lonite.  From  sodium  orthophosphate  2Na2O.BeO.P2Oc 
in  lamellae. 

1890;  12.  Wagner,  J.  Untersuchung  iiber  die  innere  Reibung 
von  Flussigkeiten. 

Ztschr.  phys.  Chem.,  5,  34. 

Uses  BeSO4.4H2O  as  one  of  the  salts  of  the  series 
studied. 

1890;  13.  Rydberg,  J.  R.  Ueber  den  Bau  der  Linienspektren 
der  chemischen  Grundstoffe. 

Ztschr.  phys.  Chem.,  5,  231. 
Refers  in  discussion  to  lines  for  beryllium. 

1890;  14.  Hautefeuille,  P.  and  Perry,  A.  Uber  verschiedene 
Silikatverbindungen  der  Oxyde  von  Kobalt,  Zinc,  Mag- 
nesium and  Beryllium. 

Chem.  Centrbl.,  1890,  II,  716. 

Bull,  de  la  soc.  franc,  de  min.,  13,  149. 
By  fusing  beryllium  sulphate  with  silicic  acid  obtained 
hexagonal  crystals  of  beryllium  oxide.     Also  obtained 
phenacite  and  a  silicate  of  the  composition,  3BeO.2SiO2. 


BIBLIOGRAPHY  OF  BERYLUUM  1 27 

1891 ;  i.  Roozeboom,  H.  W.  Bakhuis.  Ueber  die  Loslichkeit 
von  Mischkrystallin. 

Ztschr.  phys.   Chem.,   8,   528. 

Discussion  of  the  significance  of  the  mixed  crystals  of 
BeSO4.4H2O  and  BeSeO44H2O. 

1891 ;  2.     Behrens,  H.      Beitrage  zur  mikrochemischen  Analyse. 
Ztschr.  f.  Anal.  Chem.,  30,  139. 
Chem.  News,  64,  41. 

Detects  beryllium  by  means  of  the  crystals  of  its  double 
oxalate  with  potassium. 

1891 ;  3.  Winkler,  Clemens.  Ueber  die  Reduction  von  Sauer- 
stoffverbindungen  durch  Magnesium. 

Berichte,  24,  1966. 

Bull.  soc.  chim.,  (3)  6,  724. 

J  Chem.  Soc.  (London),  60,  115-5. 
Claimed  to  make  a  very  impure  BeH  by  heating  a  mix- 
ture of  BeO  and  Mg  in  H  for  four  hours.     Results 
rather  uncertain. 

1891 ;  4.  Rammelsberg,  C.  Ueber  einige  Salze  der  Unter- 
phosphorsaure. 

Sitzber.   Akad.  Wiss.    (Berlin),   1891,  369-76. 

J.  prakt.  Chem.,  (2)  45,  158. 

Chem.  Centrbl.,  1891,  II,  790. 

Bull.  soc.  chim.,  (3)  8,  686. 

J.  Chem.  Soc.  (London),  62,  404. 

Hot  solution  of  BeSO4.4H2O  when  precipitated  with 
normal  Na2PO3,  yields  2BePO3+3H2O  which  loses 
^2  of  its  water  at  23O°-25o°. 

I&91 ;  5.  Jahn,  Hans.  Ueber  die  electromagnetische  Drehung 
der  Polarizationsebene  in  Flussigkeiten,  besonders  in 
Salzlosungen. 

Ann.  der  Phys.  (Wied),  43,  284. 

Found  the  specific  rotation  for  BeSO4=o.28895. 

1891 ;  6.  Sestini,  Fausto.  Experiments  with  wheat  on  the  sub- 
stitution of  Beryllium  for  Magnesium. 


128  CHEMISTRY  OF 

J.   Chem.   Soc.    (London),  abs.    from   Staz.   sperim. 

agrar.  Ital.,  20,  256. 

Jsb.  Chem.,  1891,  2702. 

Experiments  indicate  that  beryllium  may  take  the  place 
of  magnesium  in  growth  of  wheat  but  is  not  a  complete 
substitute  for  magnesium  in  production  of  seed. 
1892;  i.     Friedel,   Ch.   and   Sarasin.     Production  artificelle   de 
divers   mineraux. 

Bibliothique  Universelle,  Arch.  phys.  nat.,  27,  145. 

Chem.  Centrbl.,  1892,  I,  864. 

Jsb.  Chem.,  1892,  520. 

Obtained  a  beryllium  aluminum  potassium  silicate  by 
fusing  the  oxide  of  the  first  two  with  potassium  silicate. 
1892;  2.     Rauter,  Gustav.     Ueber  das  Siliciumtetrachlorid. 

Ann.   der  Chem.,  270,  244. 

Jsb.  Chem.,  1892,  645. 

Heated  SiCl4  and  powdered  metallic  beryllium  in  a 
closed  tube  for  three  hours  at  240° -250°  and  found 
that  a  partial  double  decomposition  took  place  yielding 
as  a  result  a  mixture  of  SiCl4,  BeCl2,  Be  and  Si. 

1892 ;  3.     Gratzel  von  Gratz,  A.     Verfahren  zur  Gewinnung  von 
Bor,   Silicum,  Aluminium,  Beryllium  und  Magnesium. 

D.  Pat.,  58600. 

Chem.  Ind.,  14,  499. 

Ding,  polyt.  J.,  283,  129. 

Jsb.  Chem.,  1892,  2651. 

Proposes  to  mix  the  oxide  of  beryllium  with  the  chloride 
of  a  more  electro  positive  element  and  by  passing  cur- 
rent to  obtain  metal  at  one  pole  and  oxygen  at  the 
other. 

1892;  4.     McMahon,   C.   A.     Microchemical   Analyses   of   rock 
forming  mineral. 

Min.  Mag.  and  J.  of  Min.  Soc.,  10,  79-122. 
Says  the  double  salt  BeK2(SO4)2.2H2O  is  very  char- 
acteristic.    Does  not  use  the  oxalate  as  recommended 
by  Behrens    (1891 ;  2). 


BIBLIOGRAPHY  OF  BERYLUUM  I2<) 

1892;  5.  Karnojitsky,  A.  Ueber  die  optische  Anomalie  des 
Beryls. 

Ztschr.  f.  Kryst,   19,  209-219. 

Chem.  Centrbl.,  1892,  I,  492. 
Studied  the  optical  properties  of  beryl. 

1892  ;  6.  Schleir,  M.  Zur  Anwendung  des  Nitroso-/?-Naphthols 
in  der  quantitative  Analyse.  Trennung  von  Eisen  und 
Berylliums. 

Chem.  Ztg.,  16,  420. 

Chem.  Centrbl.,  1892,  I,  717. 

Jsb.  Chem.,  1892,  2540. 

Ztschr.  f.  anorg.  Chem.,  3,  84. 

Ztschr.  anal.  Chem.,  36,  699. 

Gives  details  for  analysis  of  a  mixture  of  iron  and  beryl- 
lium salts  by  precipitating  the  former  with  nitroso-/?- 
naphthol.  Excellent  quantitative  results  obtained.  Says 
that  it  is  the  best  method  of  removing  last  trace  of  iron 
from  beryllium. 
1893;  i.  Haute feuille,  P.  and  Perrey,  A. 

Annales  de  chim.  et  de  phys.,   (6)   20,  447-474. 
Artificially  produced  phenacite,  beryl  and  a  number  of 
uncertain    sodium    and    potassium    beryllium    silicates 
and  basic  beryllium  silicates. 
1893;  2.     v.  Helmolt,  Hans.     Ueber  Einige  Doppelfluoride. 

Ztschr.  f.  anorg.  Chem.,  3,  115-152. 

Jsb.  Chem.,  1893,  409. 

Obtained    BeF2.2NH4F   in    fine    crystals.     Crystallizes 
in   small   colorless   needles   and   prisms.     Prepared  by 
dissolving  Be(OH)2  in  HNH4F  to  saturation  and  evap- 
orating. 
3-     Gibson,  John. 

J.   Chem.   Soc.    (London),  63,  909. 

Chem.   Centrbl.,   1893,   I,   512,   II,  319. 

Jsb.  Chem.,  1893,  474. 

Chem.  News,  67,  66. 

Chem.  Ztg ,  17,  210. 


130  CHEMISTRY  OF   BERYLLIUM 

Ztschr.  anorg.  Chem.,  5,  240. 

Bull.  soc.  chim.,  12,  117. 

J.  Russ.  Phys.  and  Chem.  Soc.,  25,  II,  165. 
Recommends  the  preparation  of  BeO  by  igniting  beryl 
with  ammonium  hydrogen  fluoride,  which  takes  place 
at  a  low  temperature,  and  dissolving  out  with  water. 
1893;  4.     Seubert,   Karl   and     Elten,    M.     Zur   Kenntniss   der 
basischen  Metalsulfite. 

Ztschr.  f.  anorg.  Chem.,  4,  52-74,  78-81. 

Jsb.  Chem.,  1893,  312. 

J.  Chem.  Soc.  (London),  64,  456. 
Made  a  basic  sulphite  which  came  near  the   formula 
2BeSO3.9Be(OH)2.6H2O      and     a     basic     carbonate 
BeC03.5Be(OH)2.3H20. 

1894;  I.  Traube,  H.  Ueber  die  Kunstliche  Darstellung  des 
Beryll. 

Jahrb.  f.   Min.,   1894,   I ;  Mem.,  275. 

J.  Chem.  Soc.   (London),  66,  284. 
Added  sodium  silicate  to  a  solution  containing  3  mols 
BeSO4  and  one  mol  A12  (SO4)3  and  fused  the  dried 
precipitate  so  obtained  with  B2O3  in  platinum  crucible 
at  1700°  for  three  days.     Obtained  beryl  crystals. 
1894;  2.     Smith,   Edgar   F.  and  Heyl,   Paul.     Ueber  die  Ver- 
wendung  von  Quicksilber  Oxyd  bei  der  Analyse. 

Ztschr.  f.  anorg.  Chem.,  7,  88. 

Could  not  separate  Fe  and  Al  quantitatively  from  beryl- 
lium by  HgO. 

1894;  3.  Traube,  H.  Das  atomare  und  molecular  Losungs- 
volumen. 

Ztschr.  f.  anorg.  Chem.,  8,  12. 
Berichte,   27,   3 1 73-7& 
J.  Chem.  Soc.  (London),  68,  II,  70. 
Molecular  solutions  volume  of  BeSO4  and  Be(ClO3)2. 

1894;  4.  Borchers,  W.  Apparate  zur  Abschiedung  von  Mag- 
nesium, Lithium  und  Beryllium  aus  geschmolzenen 
Haloidsalzen. 


BIBLIOGRAPHY  OF  BERYLLIUM  13! 

Ztschr.  Elektrotech  and  Elektrochem.,  1894,  361. 

Chem.  Centrbl.,  1895,  I,  579. 
1894;  5.     Wyrouboff,  G.     Silicotungstates. 

Bull.  soc.  chem.,    (3)    n,   1106. 

Preliminary  note  of  work  on  silicotungstates  in  which 
he  argues  for  trivalency  of  beryllium. 

1894;  6.     Combes,  Alph.     Sur  la  valence  der  glucinium  et  la 
formule  de  la  glucine. 

Comptes  rend.,  119,  1221. 

Mon.  sci.,   (4)  9,  154. 

Ztschr.  anorg.  Chem.,  9,  245-. 

Chem.  News,  71,  38. 

Chem.  Centrbl.,  1895,  I,  320. 

J.  Chem.  Soc.   (London),  68,  224. 

Berichte,  28,  10. 

Bull.  soc.  chim.,  (3)  13,  3. 

Made  beryllium  acetylacetonate,  Be(C5H7O2)2,  by  action 
of  acetyl  acetone  on  beryllium  acetate  and  gives  its 
properties.  Melts  at  108,  sublimes  as  low  as  100°, 
boils  at  270  without  decomposition.  Two  determina- 
tions of  density  gave  figures  in  accord  with  divalency 
of  beryllium. 
1894;  7.  Walden,  P.  Ueber  die  optische  Drehung  der  lonen. 

Ztschr.  phys.  Chem.,  15,  202. 

Made  Be(C10H14BrO.SO2.O)2,  beryllium  alpha  brom 
camphor  sulphonate  and  studied  its  optical  rotation  in 
comparison  with  similar  salts  of  Mg,  Zn,  and  Ba  in 
dilute  solution.  Found  the  rotation  essentially  the  same 
for  all  (compare  1899;  J3)  an<^  f°r  tne  ac^  itself. 
These  ions  therefore  inactive. 

1895-;  I.     Wyrouboff,  G.     Response  to  remarks  of  A.  Combes  on 
valence  of  beryllium. 

Bull.  soc.  chim.,  (3)   13,  4. 
1895;  2.     Lebeau,  P.     Sur  un  carbure  du  glucinium. 

Comptes  rend.,   121,  496. 

Ztschr.  anorg.  Chem.,   13,  364. 

Chem.  Centrbl.,  1895,  II,  959. 


132  CHEMISTRY   OF    BERYLLIUM 

Bull,  soc  chim.,   (3)   13,  1065. 

Chem.  News,  72,  209. 

Mon.  sci.,   (4)   9,  806. 

Ztschr.  f.  Elektrochem.,  2,  409. 

J.  Soc.  Chem.  Ind.,  15,  141. 

J.  Chem  Soc.    (London),  70,   169. 

Berichte,  28,  899. 

BeO  mixed  with  half  its  weight  of  sugar  carbon  and  a 
little  oil  and  heated  in  an  electric  furnace  for  8-10  min- 
utes with  950  amperes  at  40  volts.  Obtained  carbide 
which  he  calls  Be4C3  (which  was  undoubtedly  Be2C) 
in  crystals,  harder  than  quartz,  transparent.  Specific 
gravity  1.9  at  15°.  Attacked  at  red  heat  by  Cl,  Br, 
HF,  and  HC1  with  liberation  of  carbon  and  formation 
of  halide.  Slowly  decomposed  water,  liberating  CH4. 
Quickly  decomposed  by  caustic  alkalies.  No  other  car- 
bide seems  to  exist. 

I895  J  3-     Lebeau,    P.     Sur   1'analyse    de   1'emeraude. 

Comptes  rend.,  121,  601. 

Chem.  News,  72,  245. 

Dissolved  in  KOH  in  silver  crucible  and  afterward  fol- 
lowed procedure  of  Debray. 

1895;  4.     Rowland,  H.  A.  and  Tatnall,  R.  R.     The  arc  spectra 
of  the  elements.     II.  Boron  and  Beryllium. 

Astrophysical  Journal,  1895,  I,  16;  II,  185. 
Gives  as  the  most  prominent  lines  for  Be  between  2100 
and  4600  the  following : 

2348.697 

2350.855 

2494-532 

2494.960  Observations  made  by  means 

2650.414  of    a     grating    of    21^    feet 

2651.042  radius  and  20000  lines  to  the 

3I3°-556  inch   on   photographic    plate 

3131.200  19  inches  in  length. 

3321.218 

3321.486 

4572.869 


BIBLIOGRAPHY  OF  BERYUJUM  133 

l&95  >  5-     Lebeau,  P.     Sur  la  traitement  de  I'emeraude  et  la  prep- 
aration de  la  glucine  pure. 

Comptes  rend.,  121,  641. 

Ztschr.  anorg.  Chem.,  13,  364. 

Bull.  soc.  chim.,   (3)    15,    166. 

Chem.  News,  73,  3. 

Mon.  sci.,   (4)    10,  71. 

Ztschr.  f.   Elektrochem.,  2,  432. 

Chem.  Centrbl.,  1895,  II,  1150. 

J.  Chem.  Soc.  (London),  70,  168. 
Decomposed  beryl  by  fusion  with  twice  its  weight  of 
CaF2,  when  on  pouring  into  water,  a  friable  mass, 
easily  attacked  by  H2SO4,  was  obtained.  Most  of  the 
silica  was  thereby  removed.  Also  fused  beryl  in  an 
electric  furnace  and  volatilized  part  of  its  silica  when 
residue  was  easily  attacked  by  a  mixture  of  H2SO4 
and  HF.  Impure  beryllium  carbonate  obtained  by 
usual  procedure  was  dissolved  in  HNO3,  iron  precipi- 
tated by  ferrocyanide,  the  excess  ferrocyanide  by  cop- 
per nitrate  and  the  copper  by  H2S.  The  solution  was 
then  mixed  with  ammonia  and  the  precipitate  allowed 
to  stand  three  days  whereby  the  A1(OH)3  became  in- 
soluble in  ammonium  carbonate. 

1895  ;  6.     Hart,  Edward.     Note  on  the  Purification  of  Glucinium 
Salts. 

J.  Amer.  Chem,  Soc.,  17,  604. 

Chem.  Centrbl.,  1895,  II,  590. 

Bull.  soc.  chim.,   (3)   16,  226. 

Chem.  News,  72,  77. 

J.  Chem.  Soc.  (London),  70,  168. 

Separates  beryllium  from  iron  and  aluminum  by  dissolv- 
ing in  H2SO4  and  adding  Na2CO3  slowly,  with  boiling 
after  each  addition,  until  the  liquid  shows  no  yellow 
color.  The  beryllium  remains  in  solution  as  a  basic  sul- 
phate while  the  iron  and  aluminum  are  precipitated. 


134  CHEMISXRY  OF   BERYLUUM 

1895;  7.     Prudhomme,  Maurice.     Sur  le  mordant  de  glucine. 

Bull.  soc.  chim.,  (3)   13,  509. 

Mon.  sci.,  (4)  9,  411. 

Ztschr.  f.  anorg.  Chem.,  10,  446. 

Chem.  Centrbl.,  1895,  II,  264. 

J.  Soc.  Chem.  Ind.,  14,  802. 

Beryllium  acts  as  a  divalent,  not  as  a  trivalent  element. 
1895 ;  8.     Henry  Louis.     Apropos  un  carbure  du  glucinium. 

Comptes  rend.,  121,  600. 

Ztschr.  f.  anorg.  Chem.,  13,  365. 

Bull.  soc.  chim.,  15,  165,  475. 

Chem.  Centrbl.,  1895,  II,  1067. 

Bull.  acad.  Belg.,  30,  460-465. 

Chem.  News,  72,  245. 

J.   Chem.   Soc.    (London),  70,    169. 

Mon.  sci.,  (4)  9,  857. 

Berichte,  28,  967. 

J.  Soc.  Chem.  Ind.,  15,  141. 

Criticises  Lebeau  (1895  ;  2)  for  giving  formula  Be4C3  to 
his  carbide  and  using  atomic  weight  of  13.8  when 
analyses  agreed  with  Be2C  and  valency  of  beryllium 
had  been  proven. 

1895;  9.     Atkinson,  E.  A.  and  Smith,  E.  F.     The  Separation  of 
Iron  from  Beryllium. 

J.  Amer.  Chem.  Soc.,  17,  688. 

Chem.  Centrbl.,  1895,  II,  844. 

Bull.  soc.  chim.,  (3)  16,  229. 

Ann.  de  chim.  analytique,  i,  118. 

J.  Chem.  Soc.  (London),  70,  220. 

Analyst,  21,  23. 

Showed  that  iron  and  beryllium  can  be  quantitatively 
separated  by  Nitroso-£-Naphthol.     (Compare  1892;  6). 
1895;  10.     Warren,  H.  N.     Manufacture  and  Commerical  Sep- 
aration of  Glucinium. 

Chem.  News,  72,  310. 

Ztschr.  f.  anorg.  Chem.,  13,  364. 

Ztschr.  f.  Elektrochem.,  2,  459. 


BIBLIOGRAPHY  OF  BERYLLIUM  135 

Chem.  Centrbl.,  1896,  I,  336. 
-  J.  Chem.  Soc.   (London),  70,  247. 
Proposed  separation  of  the  metal  by  electrolytic  reduc- 
tion of  the  bromide.     Bromide,  however,  is  a  non  con- 
ductor. 

1895-;  ii.     Borchers,  W.     Abschiedungsmethoden  des  Lithiums 
und  des  Berylliums. 

Ztschr.  f.  Elektrochem,  2,  3,  9. 

Chem.  Centrbl.,  1895,  II,  13. 

J.  Chem.  Soc.   (London),  70,  521. 

Ztschr.  phys.  Chem.,  21,  517. 

Proposes  to  electrolyze  a  melted  mixture  of  BeCl2  with 
alkaline  chlorides  or  alkaline  earth  chlorides.  Makes 
mixture  by  evaporating  mixed  chlorides  and  adding  a 
little  NH4C1  to  arrest  conversion  of  BeCl2  into  BeO. 
Calcium  and  magnesium  chlorides  must  be  absent.  No 
metal  appears  to  have  been  made. 

1895 ;  12.     Rinne,   F.     Die   Krystallform   chemischen  .einfacher 
Korper. 

Ztschr.  phys.  Chem.,   16,  529. 

Gives  crystal  form  data  for  Be  and  BeO  in  table  with 
many  other  substances. 
1896;  I.     Wyrouboff,  G.     Silicotungstates. 

Bull.  soc.  franc,  d.  min.,  19,  219,  354. 

Ztschr.  f.  Kryst,  29,  676. 

J.  Chem.  Soc.  (London),  72,  178. 
Made  beryllium  silico  tungstate  to  which  he  gave  the 
formula  Be1(W12SiO40)3.     Crystallizes  below  45-°  as  a 
cubic   hydrate   containing  93   H2O;   above   45°,    as   a 
rhombohedral  hydrate  containing  87  H2O.     In  presence 
of  nitric  acid  at  30°  a  45  H2O  is  obtained. 
1896;  2.     Properties  of  Beryllium. 

Eng.  and  Mining  J.,  6,  162  from  Electrical  Review 

of  London. 

Revue  de  chim.  ind.,  7,  323. 

Claims  beryllium  is  on  the  market  at  $18  a  pound  and 
gives  very  improbable  properties  for  metal. 


136  CHEMISTRY  OF   BERYLLIUM 

1896;  3.     Liebermann,  Louis.     Verfahren  zur  Darst.  von  Beryl- 
lium in  form  seiner  Legierungen. 

D.  R.  P.  94507,  Sept.  22,  '96,  Patent  bl.  18868. 

Chem.  Ztg.,  23,  253. 

Berg,  in  Hutten  Ztg.,  57,  149. 

Wagners  Jsb.,  43,  320. 

Ztschr.  f.  Elec.,  4,  258. 

1896;  4.     Retgers,  J.  W.     Beitrage  zur  Kenntniss  des  Isomor- 
phisms. 

Ztschr.  f.  phys.  Chem.,  20,  481. 

Ztschr.  f.  Kryst,  30,  635'. 

Amer.  J.  ScL,  (4)  2,  448. 

J.  Chem.  Soc.   (London),  72,  17. 

Berichte,  29,  1059. 

By  discussion  of  the  results  of  others  and  by  crystalliz- 
ing mixtures  of  the  sulphates  of  Cu,  Ni,  Fe,  Mn  and 
Be,  Retgers  comes  to  the  conclusion  that  Be  is  not 
isomorphous  with  the  metals  of  the  Mg.  group. 
1896;  5.  Duboin,  Andre.  Sur  une  methode  de  reproduction 
de  silicates  doubles  de  potasse  et  d'autres  bases. 

Comptes  rend.,  123,  698. 

Chem.  Centrbl.,  1896,  II,  1081. 

J.  Chem.  Soc.   (London),  72,  96. 

Obtained  crystals  of  a  double  silicate  of  Be  and  K  which 
appear  homogeneous  but  vary  between 
2K2O.3BeO.5SiO2  and 
2K2O.3BeO.7SiO2, 

made  by  dissolving  a  mixture  of  BeO  and  SiO2  in 
fused  KF  and  then  submitting  to  long  fusion  with 
KC1. 

1896;  6.     Lebeau,    P.     Sur   quelques  proprieties  de   la  glucine 
pure. 

Comptes  rend.,  123,  818. 

Chem.  Centrbl.,  1897,  I,  16. 

Ztschr.  anorg.  Chem.,  15,  472. 

Chem.  Ztg.,  20,  973;  21,  8. 

Chem.  News,  74,  292. 


BIBLIOGRAPHY  OF  BERYLLIUM  137 

J.  Soc.  Chem.  Ind.,  16,  72. 
J.  Chem.  Soc.   (London),    72,   144. 
J.  Russ.  Phys.  and  Chem.  Soc.,  29,  II,  58. 
Specific  gravity  BeO  ignited  at  44O°=3,oi2,  ignited  at 

I2OO°=3.OI. 

BeO  fuses  in  electric  arc  and  on  cooling  forms  a  white 
crystalline  mass,  slightly  harder  than  rubies.  BeO  is 
attacked  by  fluorine  when  heated  but  not  by  other  halo- 
gens or  by  sulphur  or  nitrogen. 

Potassium,  sodium  and  aluminum  have  no  action  on  the 
oxide  at  high  temperatures  and  it  is  not  reduced  by 
magnesium  even  at  the  boiling  point  of  that  metal. 
BeO  swells  up  in  pure  H2SO4  and  yields  anhydrous 
sulphate  which  dissolves  very  slowly  in  boiling  H2O. 
1896;  7.  Burgass  Rob.  Anwendung  des  Nitroso-/?-Naphthols 
in  der  anorganische  Analyse. 

Ztschr.  angwdte.  Chem.,  1896,  596. 

J.  Chem.  Soc.  (London),  72,  163. 

Separates  quantitatively  iron  from  beryllium  by  means 
of  Nitroso-#-Naphthol. 
Compare  1892;  6  and  1895;  9. 

1896;  8.     Glaser,    Charles.      Chemical    Analysis    of    Monazite 
Sand. 

J.  Amer.  Chem.  Soc.,  18,  782 

J.  Chem.  Soc.  (London),  72,  191. 

Rev.  Amer.  Chem.  Research,  2,  66. 
Gives  his  method  for  determining  beryllium  in  monazite. 
1896;  9.     Anonymous. 

Beryllium     instead    of     platinum     for     incandescent 

lamps. 

Elektrochem.  Ztschr.,  3,  70,  from  Journal  des  inven- 

teurs. 

Suggests  use  as  indicated  by  title.     Coefficient  of  expan- 
sion not  given. 
1896;  10.     Larssow,   Aksel.     Untersuchung  iiber  Niob. 

Ztschr.  f.  anorg.  Chem.,  12,  188. 

J.  Chem.  Soc.  (London),  70,  564. 


138  CHEMISTRY  OF   BERYLUUM 

Made  a  crystalline  beryllium  columbate  by  fusing  with 
boric  anhydride,  the  precipitate  obtained  by  precipitat- 
ing potassium  columbate  with  beryllium  chloride. 
Found  composition,  6.24  per  cent.  BeO,  89.60  per  cent. 
Cb205. 

1896;  ii.     Gladstone,  J.  H.     The  Relation  between  the  refrac- 
tion of  elements  and  their  chemical  equivalents. 

Proc.  Roy.  Soc.,  60,  140-146. 

Ztschr.  phys.  Chem.,  22,  648. 
Specific  refraction  Be=-733. 
Atomic  refraction  Be=6.6. 

1896;  12.     Ortloff,  W.     Beitrage    zur    Kenntniss    eutropischer 
Reihen. 

Ztschr.  phys.  Chem.,  19,  201. 
Quote  physical  properties  in  discussion. 

1897;  I.     Havens,   Franke    S.     The   Separation   of  Aluminium 
and  Beryllium  by  the  action  of  Hydrochloric  Acid. 

Amer.  J.  of  Sci.,   (4)  4,  111-114. 

Chem.  Centrbl.,  1897,  II,  810. 

Bull.  soc.  chim.,  (3)  18,  1129. 

Chem.  News,  76,  in    (complete). 

Analyst,  23,  109. 

Separates  Be  and  Al  quantitatively  by  means  of  the  in- 
solubility of  A1C13.6H2O  in  ether  and  water  (1:1), 
saturated  wtih  HC1  gas. 

1897;  2.     Havens,   Franke   S.     Trennung  von   Aluminium   und 
Beryllium  durch  Salzsaure. 

Ztschr.  anorg.  Chem.,  16,  15-18. 

Chem.  Centrbl.,  1898,  I,  476. 

Bull  soc.  chim.,  (3)  26,  163. 

J.  Chem.  Soc.    (London),  74,    142. 
Same  as  1897;  i. 

1897;  3.     Woge,  Paul.     Ueber  die  Wertigkeit  des  Berylliums. 

Inaugural  Dissertation,   (Berlin),  1897. 
See  1897;  4. 


BIBLIOGRAPHY  OF  BERYUJUM  139 

1897;  4.     Rosenheim,  A.  and  Woge,  P.     Ueber  die  Wertigkeit 
des  Berylliums. 

Ztschr.  f.  anorg.  Chem.,  15,  283-318. 

Bull.  soc.  chim.,  (3)  20,  308. 

J.  Phys.  Chem.,  2,  400. 

Chem.  Centrbl.,  1897,  II,  1131. 

Chem.  News,  78,  160. 

J.  Chem.  Soc.  (London),  74,  71. 

Extensive  research  on  the  oxalates,  tartrates,  molybdates 
and  sulphites  of  beryllium  to  show  their  differences  from 
the  corresponding  salts  of  Al,  Fe  and  Cr,  ending  with 
the  preparation  of  BeCl2  and  the  determination  of  its 
molecular  weight  in  pyridine  by  the  boiling  point 
method. 
The  following  substances  were  prepared: 

K2O,2BeO,2C2Os -f  2^H2O,1  These  were  obtained  in  crystalline 
Na2O,2BeO,2C2O3  +  5H2O,      (.forms  and  seem  to  be  definite  basic 
(NH4)2O,2BeOv2C2O3  -f  2>£H2O,  J  compounds, 
K2O,BeO,2C2O3  +  H2O, 
Na2O,  BeO,2C2O3  +  H2O, 
(NH4)2O,BeO,  2C2O3, 
2BeO.3C2O3  +  6H2O, 
BeC204  +  3H20, 
K2O,4BeO,2C4H4O5  -f-  8H2O, 
NajCUBeCMC^Og  -f  8H2O, 
(NH4)20,4BeO,2C4H405  +  8H2O, 
K2O.2BeO,2C4H4O5  +  2H,O, 
BeO,MoO3.2H2O, 

io(2BeO.MoO3)  +  2(NH4)2O,3MoO3  -f  i8H2O, 
K20,2BeO,3S02  +  9H,O, 
(NH4)20,2BeO,3S02  +  4H2O. 

l%97>  5-     Heusler,  Fr.     Die  Chemie  bei  der  Temperature  des 
elektrischen  Lichtbogens. 

Ztschr.  anorg.  Chem.,  14,  173. 

Compilation  of  the  work  on  carbides  including  that  of 
beryllium. 

1897 ;  6.     Gladstone,   J.   H.   and   Hibbert,   W.     The   Molecular 
Refraction  of  dissolved  Salts  and  Acids. 
J.  Chem.  Soc.   (London),  71,  823. 


I4O  CHEMISTRY  OF   BERYLLIUM 

Compared  the  molecular  refraction  of  solid  and  dis- 
solved BeSO44H,O. 

Molecular  refraction  of  solid=47.4i. 
Molecular  refraction  of  liquid=47.94. 

1897;  7.  Mosnier,  A.  Sur  quelques  combinaisons  de  1'iodure 
de  plomb  avec  d'autres  iodures  metalliques  ou  organi- 
ques.  lodure  double  de  plomb  et  de  glucinium. 

Ann.  de  chim.  et  de  phys.,  (7)   12,  374-426. 

J.  Chem.  Soc.  (London),  76,  222. 

Treated  carbonate  of  beryllium  with  concentrated  HI, 
then  added  lead  iodide  as  long  as  it  dissolved.  By 
cooling,  obtained  fine  yellow  needles  decomposed  by 
water.  From  analysis  he  calculates  the  formula 
Be2I6.3PbI2,  ioH20. 

1897;  8.  Lebeau,  P.  Sur  la  preparation  des  alliages  de  glucin- 
ium. Allaiges  de  glucinium  et  de  cuivre. 

Comptes  rend.,  125,  1172. 

Bull.  soc.  chim.,  (3)   19,  54. 

Chem.  Centrbl.,  1898,  I,  310. 

Chem.  Ztg.,  22,  17. 

Ztschr,  anorg.  Chem.,  19,  351. 

J.  de  pharm.  et  de  chim.,  (6)  7,  240. 

Chem.  News,  77,  44. 

J.  Chem.  Soc.  (London),  74,  292. 

J.  Soc.  Chem.  Ind.,  17,  1152. 

Owing  to  the  ease  with  which  Be  and  C.  combine  at 
high  temperatures,  the  metal  can  not  be  reduced  from 
its  oxide  in  the  electric  arc.  Alloys  can  be  prepared 
however,  by  reducing  BeO  in  this  manner  in  contact 
with  other  metals  or  metallic  oxides.  Prepared  alloys 
with  Cu,  Cr,  Mo  and  W,  but  describes  those  of  copper 
only.  With  10  per  cent,  of  Be  the  copper  alloys  are 
pale  yellow,  almost  white.  With  5  per  cent.  Be  they 
are  yellow,  easily  polished  and  malleable  cold  or  hot.  As 
low  as  5  per  cent.  Be  alters  appearance  of  Cu  and  makes 
it  sonorous.  Alloy  of  1.32  per  cent,  is  golden  yellow 
and  can  be  easily  filed  and  forged. 


BIBLIOGRAPHY  OF  BERYLUUM  14! 

1898;  i.     Lebeau,  P.     Recherches  sur  le  glucinium  et  ses  com- 
poses. 

Academic  Dissertation,  Paris,  1898. 

1898;  2.     Lebeau,  P.  Sur  un  procede  de  preparation  des  bronzes 
de  glucinium. 

Bull.  soc.  chim.,  (3)  19,  64. 

Chem.  Centrbl.,  1898,  I,  496. 
See  1897;  8. 

1898;  3.     Lebeau,  Paul.     Preparation  du  glucinium  par  electro- 
lyze. 

Comptes  rend.,  126,  744. 

Chem.  Centrbl.,  1898,  I,  879. 

Chem.  News,  77,  173. 

J.  Phys.  Chem.,  3,  185. 

Amer.  J.  Sci.,  (4)  7,  155. 

Zeit  f.  Elec.,  5,  31. 

Bull.  soc.  chim.,  (3)   19,  409. 

Chem.  Ztg.,  22,  245. 

J.  Chem.  Soc.   (London),  74,  511. 

J.   de  phar  et  de  chim.,    (6)    7,  345. 

J.  Soc.  Chem.  Ind.,  17,  386. 

Obtained  metallic  beryllium  by  electrolysis  of  BeF2.NaF 
in  nickel  crucible.  Melted  over  bunsen  burner  and  then 
passed  current  of  6-9  amperes  at  35-40  volts  removing 
source  of  heat.  Made  salt  by  fusing  exact  equivalents 
i- 1  of  the  two  fluorides.  Nickel  crucible  negative  pole 
and  graphite  stick  positive  pole. 

1898;  4.     Lebeau,  Paul.     Gewinnung  von  Beryllium  durch  Elec- 
trolyze.     Beryllium  Legierungen. 

Elektrochemische  Zeitschrift,   5,    in. 

Chem.  Centrbl.,  1898,  II,  750. 

J.  Soc.  Chem.  Ind.,  17,  155. 

Amer.  Chem.  J.,  27,  487. 

Article  is  fully  as  complete  as  1898;  3  and  much  the 
same  in  character  although  a  separate  communication 
Says  Nilson  and  Petterssen  found  BeCl2  to  be  a  non- 
conductor, which  he  confirmed  and  found  same  to  be 


142  CHEMISTRY  OF   BERYLLIUM 

true  of  the  bromide  and  fluoride.  Added  NaF  to  make, 
mixture  conduct  electricity.  Used  nickel  crucible  and 
carbon  anode  with  a  current  of  20  amperes  and  80  volts 
(vide  1898;  3).  Heated  first  with  bunsen  burner  but 
later  controlled  heat  by  current  alone.  Kept  at  low 
redness.  Fine  hexagonal  Be  obtained  free  from  iron 
and  nickel  \\ith  a  specific  gravity  of  1.73  at  15°.  Gives 
properties  of  beryllium. 

Made  alloys  with  copper  and  gives  their  properties. 
One-half  per  cent.  Be  makes  copper  quite  sonorous. 
1.32  per  cent.  Be  in  copper  is  a  gold  yellow  metal  and 
finely  sonorous. 

1898;  5.     Lebeau,  Paul.      Sur  le  traitement  industriel  de  1'emer- 
aude  au  feur  electrique. 

Comptes  rend.,  126,  1202. 

Bull.  soc.  chim.,  (3)  19,  940. 

Ztschr.  f.  Elek.,  5,  39. 

Chem.  News,  77,  285. 

Chem.  Ztg.,  22,  380. 

Heated  beryl  in  carbon  tube  in  electric  furnace  at 
95  amperes  and  50  volts  for  ten  minutes  and  dissolved 
in  hydrofluoric  acid.  This  removes  silicon  and  alumin- 
um since  A1F3  is  insoluble.  Solution  worked  up  for 
beryllium  as  ordinarily. 

1898;  6.     Lebeau,  Paul.     Sur  1'iodure  de  glucinium. 

Comptes  rend.,  126,  1272. 

Bull.  soc.  chim.,  (3)  19,  800. 

Chem.  Centrbl.,  1898,  II,  85. 

Ztschr.  phys.  Chem.,  28,  570. 

Chem.  News.,  77,  266. 

J.  phar.  ciiim.,  (6)  7,  592- 

J.  Chem.  Soc.   (London),  74,  580. 
Made  BeI2  by  action  of  iodine  on  the  carbide  and  stud- 
ied its  properties  exhaustively. 

Specific  gravity  4.20,  fuses  at  510°  and  begins  to  sub- 
lime at  once,  boils  585-595°. 


BIBLIOGRAPHY  OF  BERYUJUM  143 

Insoluble  in  benzine  and  toluene,  soluble  in  carbon  disul- 

phide. 

Attacked  violently  by  water  and  decomposed  by  flourine, 

chlorine  and  bromine. 

1898;  7.     Lebeau,  Paul.       Sur  un  borocarbure  de  glucinium. 

Comptes  rend.,  126,  1347. 

Bull.  soc.  chim.,  (3)  19,  823. 

Chem.  Centrbl.,  1898,  II,  86. 

Chem.  Ztg.,  22,  425. 

Ztschr.  f.  Elek.,  5,  91. 

Chem.  News,  77,  289,  (complete). 

J.  Chem.  Soc.   (London),  74,  581. 
Prepared  3Be2C.Bo6C  by  heating  a  mixture  of  BeO  and 
B  in  a  carbon  crucible  in  the  electric  furnace.     Crys- 
talline with  specific  gravity  of  2.4. 

1898;  8.  Lebeau,  Paul.  Sur  la  preparation  et  les  proprieties 
du  fluorure  de  glucinium  anhydre  et  de  1'oxyfluorure  de 
glucinium. 

Comptes  rend.,  126,  1418. 

Bull.  soc.  chim.,   (3)   19,  824. 

Chem.  News,  77,  288,   (complete).    ' 

Ztschr.  f.  Elek.,  5,   118. 

Made  BeF2  by  evaporating  a  solution  .of  Be(OH)2  in 
excess  of  HF  and  drying  in  HF  gas  in  platinum  tube, 
obtaining  thereby  a  transparent  glassy,  deliquescent 
fluoride,  if  he  raised  heat  to  drive  off  all  the  water,  he 
obtained  a  basic  residue  of  approximate  £  BeF.2BeO  but 
different  analyses  did  not  agree  closely.  Made  purest 
BeF2  by  heating  BeF2.NH4F  in  platinum  tube  in  CO2 
gas.  Anhydrous,  glassy,  sublimes  in  little  transparent 
crystals  above  800°,  specific  gravity  2.1.  Soluble  in 
H2O  and  in  90  per  cent,  alcohol.  Attacked  by  H2SO4. 

1898;  9.     Hober,   Rudolf  and    Kiesow,    Friedrich.     Ueber   den 
Geschmack  von  Salzen  und  Laugen. 
Ztschr.  phys.  Chem.,  27,  601. 
Chem.  Centrbl.,  1899,  I,  332. 


144  CHEMISTRY  OF   BERYLLIUM 

Found  that  BeCl2  and  BeSO44H2O  have  the  same  sweet 
taste  at  equal  cation  concentrations. 

1898;  10.  Boudard,  O.  Sur  les  sables  monazites  de  la  Caro- 
lina du  Nord. 

Bull.  soc.  chim.,  (3)   19,  10. 

Chem.  Centrbl.,  1898,  I,  435. 

Gives  method  of  analyzing  monazite  including  separa- 
tion of  beryllium. 

1898;  ii.  de  Gramont,  A.  Analyse  spectrale  des  mineraux 
nonconducteurs  par  les  sels  fondus. 

Bull,  de  la  soc.  franc,  de  min.,  21,  109. 

Comptes  rend.,  126,  1513. 

Ztschr.  f.  Kryst,  32,  637. 

J.  Chem.  Soc.   (London),  74,  636. 
Obtains  the  blue  line,  457.3  easily  in  spark  spectra  by 
fusing  beryl  with  lithium  carbonate. 

1898;  12.  Curtius  and  Rissom.  Neue  Untersuchungen  iiber 
den  Stickstoffewasserstoff  N3H. 

J.  f.  prakt.  Chem.,  58,  292. 

J.  Chem.  Soc.,  76,  92. 

Attempts  to  make  (N3)2Be  by  action  of  (N3)2Ba 
upon  BeSO4  but  failed  as  it  immediately  broke  down 
into  N3H  and  Be(OH)2. 

1898;  13.  Florence,  W.  Darstellung  mikroskopischer  Krystalle 
in  Lothrohrperlen. 

Ztschr.  f.  Kryst,  33,  180. 

1898;  14.  Goldschmidt,  Dr.  Hans.  Ueber  em  Neues  Verfahren 
sur  Darstellung  von  Metallen  und  Legeierungen  und 
von  Korund,  sowie  zur  Erzielung  hoher  Temperaturen. 

Ztschr.  angewandte  Chem.,  1898,  822. 
Claims  that  Lebeau  is  wrong  and  that  BeO  is  at  least 
reduced  in  part  by  Al  but  comes  in  fine  powder  mixed 
with  the  slag.  His  proof  is,  however,  simply  that  the 
mass  grows  dark  and  on  ignition  becomes  white  again 
and  is  far  from  convincing. 


BIBLIOGRAPHY  OF  BERYUJUM  145 

1898;  15.     Liebermann,  Louis.     Verfahren  sur  Darstellung  von 
Beryllium,  D.  R.  P.   101326. 

Patent  bl.  20,  193. 

Chem.  Ztg.,  23,  525. 

Ztschr.  f.  Elek.,  5,  366. 

Chem.  tech.  Rep.,  38,  120,  254. 

Electr.  Chem.  Ztg.,  6,  81. 

Chem.  Centrbl.,  1899,  I,  1096. 
Details  of  a  patent  of  very  doubtful  value. 

1898;  16.     Liebermann,  Louis.     Verfahren  zur  Darstellung  von 
Beryllium,  D.  R.  P.  104632. 

Patent  bl.,  20,  816. 

Chem.  Ztg.,  23,  944. 

Ztschr.  f.  Elektr.  Chem.,  6,  284. 

Electro.  Chem.  Ztg.,  6,  222. 

Ztschr.  f.  Elek.,  5,  428. 

Chem.  Tech.  Rep.,  38,  456  . 

Chem.  Centrbl.,  1899,  II,  1073. 
Patent  of   very   doubtful   value. 
1898;  17.     Roman,  R.  J.     Beryllium  Legierungen. 

Chem.  Ztg.,  22,  83. 

Claims  priority  over  both  Liebermann  and  Lebeau. 
1898;  18.     Moissan.     Electrolytische  Darstellung  von  Beryllium 
und  zeiner  Legierungen  und  Darstellung  von  Beryllium 
Legierungen  in  Elektrischen  Ofen. 

Chem.  Ztg.,  22,  650. 

Report  of  Lebeau's  work  before  section  on  Elektro- 
chemistry  of  International  Congress  of  Applied  Chemis- 
try, Vienna  1898. 

1898;  19.     Van  Bemmelen,  J.  M.      Die  Absorption.     Unsetzung 
der  Krystallinischen  Hydrate  in  amorphe  Substanzen. 

Ztschr.  f.  anorg.  Chem.,  18,  126. 

Effects  of  heat  on  the  "crystalline"  and  colloidal  beryl- 
lium hydrate. 

1898;  20.     Franck,  Leon.     Studien  iiber  Aluminium  als  Reduc- 
tionsmittel. 

Chem.  Ztg.,  22,  244. 

10 


146  CHEMISTRY  OF   BERYUJUM 

Claims  that  by  heating  BeO  and  Al  in  closed  glass  tube 
a  reduction  takes  place,  but  gives  no  proof  of  the  fact 
except  that  a  gray  mass,  attacked  by  nitric  acid,  was 
formed. 

Probably  incorrect  as  Lebeau  has  shown. 

1899;  I-  Petersen,  .  Note  on  preparation  of  pure  beryl- 
lium oxide. 

Chem.  Ztg.,  23,  439. 

1899;  2.  Meyer,  Stefan.  Ueber  die  Magnetischen  Eigenschaf- 
ten  der  Elements  (Beryllium). 

Monatshefte,  20,  372. 

Ann.   der  Phys.   (Wied.),  68,  324. 

J.  Chem.  Soc.  (London),  76,  587. 

Chem.  Centrbl.,  1899,  II,  163,  740. 
Gives  the  magnetic  susceptibility  of  beryllium  as  directly 
observed  at  15°  as  -f  33.8  X  io~6  in  absolute  units  and 
atomic  susceptibility  for  i  gram  per  liter  as  -f -72X  io~*. 
1899;  3.  Meyer,  Stefan.  Magnetisirungszahlen  anorganische 
Verbindung. 

Monatshefte,  20,  799. 

Ann.  der  Phys.   (Wied.),  69,  236. 

Chem.  Centrbl.,  1900,  I,  5. 

J.  Chem.  Soc.  (London),  78,  7. 

Determined    the  magnetic    susceptibility    of    beryllium 
chloride,  oxide,  hydroxide,  carbonate  and  sulphate. 
1899;  4.     Pozzie-Escot,  M.  E.     Analyse  microchimique. 

Ann.  de  chim.  anal.,  4,  377. 

Determines  beryllium  microscopically  by  crystals  of  the 
double  oxalate  of  beryllium  and  potassium.  Drawing 
of  crystals  given  in  original. 

1899;  5.  Havens,  F.  S.  and  Way,  A.  F.  Separation  of  Iron 
from  Chromium,  Zirconium  and  Beryllium  by  the 
Action  of  Gaseous  Hydrochloric  Acid  on  the  Oxides. 

Amer.  J.  of  Sci.,  (4)  8,  217. 

J.  Chem.  Soc.  (London),  78,  50. 

Removes  iron  by  hydrochloric  acid  gas  mixed  with  a 
little  chlorine  at  temperatures  so  low  as  200-300°. 


BIBLIOGRAPHY  OF  BERYLLIUM  147 

Higher  temperatures  act  quicker — but  if  much  iron  is 
present  some  of  the  beryllium  may  be  carried  away 
mechanically. 

1899;  6.  Havens,  F.  S.  and  Way,  A.  F.  Die  Trennung  des 
Eisens,  von  Chrom,  Zircon  und  Beryllium  durch  die 
Einwirkung  von  gasformiger  Salzsaure  auf  die  Oxyde. 

Ztschr.  f.  anorg.  Chem.,  21,  389. 

Review  Amer.  Chem.  Research,  5,  102. 

Analyst.,  25,  23. 

Same  as  1899;  5  but  separately  transmitted. 
1899;  7.     Liebermann,  L.     Beryllium  Legierungen. 

Chem.  Ztg.,  24,  43. 
Claims  priority  over  Lebeau. 

1899;  8.  Austin,  Martha.  The  double  Ammonium  Phosphates 
of  Beryllium,  Zinc  and  Cadmium  in  Analysis. 

Amer.  J.  of  Sci.,  (4)  8,  206-216. 

Chem.  Centrbl.,  1899,  II,  791. 

J.  Chem.  Soc.   (London),  78,  49. 

Rev.  Amer.  Chem.  Res.,  5,  102. 

J.  Soc.  Chem.  Ind.,  19,  72. 

Shows  that  the  precipitation  of  beryllium  as  ammonium 
beryllium  phosphate  and  ignition  to  the  pyrophosphate 
does  not  give  uniform  results. 

1899;  9.  Austin,  Martha.  Die  Ammoniumdofpelphosphate 
von  Beryllium,  Zinc  and  Cadmium  in  analytische  Bezie- 
hung. 

Ztschr.  anorg.  Chem.,  22,  207-220. 

Chem.  Centrbl.,  1899,  II,  1032. 
Same  as  1899;  8  but  separately  transmitted. 

1899;  10.  Ley,  H.  Studien  iiber  die  hydrolytische  Dissocia- 
tion der  Salzlosungen. 

Ztschr.  phys.  Chem.,  30,  II,  218. 

Chem.  Centrbl.,  1899,  II,  ion. 

J.  Chem.  Soc.  (London),  78,  II,  67. 
Says  basicitv  of  Be(OH)2  is  eleven  times  as  great  as 
that  of  A1(OH)3.  Found  beryllium  salts  not  so  strongly 


148  CHEMISTRY  OF   BERYLLIUM 

hydrolyzed  as  aluminum  salts.  Used  inversion  method. 
Worked  on  sulphate  and  chloride. 

1899;  ii.  Lebeau,  P.  Recherches  sur  le  glucinium  et  ses  com- 
poses. 

Ann.  die  chim.  et  de  phys.,  (7)   16,  457-503. 

Chem.  Centrbl.,  1899,  I,  963. 

J.  Phys.  Chem.,  4,  222. 

J.   Chem.    Soc.    (London),   76,    554. 

Ztschr.  anorg.  Chem.,  21,  86. 

Ztschr.  f.  Kryst,  34,  629. 

This  is  a  resume  of  all  of  Lebeau's  work  on  beryllium 
and  is  the  best  and  most  comprehensive  article  written 
on  beryllium  and  its  compounds. 

1899;  12.  Woulff,  G.  Optische  Studien  an  pseudosymmetris- 
chen  Krystallen,  Das  Beryllium  Sulfat. 

Ztschr.   f.  Kryst.,   17,  592. 

Chem.  Centrbl.,  1900,  II,  73. 

BeSO4.4H2O  is  strongly  double  refractive.  The  crys- 
tals are  negative  and  uniaxial. 

1899;  13.  Rosenheim,  A.  u.  Itzig,  H.  Ueber  einige  complexe 
Salz  der  Weinsaure  und  Apfelsaure  und  ihr  specifische 
Drehungsvermogen. 

Berichte,  32.  3424. 

Chem.  Centrbl.,  1900,  I,  170. 

Bull.  soc.  chim.,  (3)  24,  520. 

J.  Chem.  Soc.   (London),  78,  135. 

J.  Russ.  Phys.  and  Chem.  Soc.,  32,  II,  57. 
Worked  on  the  mono-  and  diberyllium  tartrates  of  Ros- 
enheim and  Woge  (1898;  4)  to  determine  their  molecu- 
lar rotation  and  found  that  the  introduction  of  beryl- 
lium into  the  molecule  greatly  increased  the  rotatory 
power  whether  right  or  left.  Diberyllium  tartrate 
showed  a  molecular  rotatory  power  of  225°-242°  not 
effected  by  dilution.  Monoberyiljlium  tartrate  gave  ro- 
tation of  125°. 

Made  double  mallates  with  beryllium  to  correspond  to 
the  tartrates  before  described. 


BIBLIOGRAPHY  OF  BERYLLIUM  149 

Addition  of  beryllium  sulphate  does  not  effect  rotatory 
power  of  dextrose,  or  chlorosuccinic  acid. 

1899;  14.  Amphola  and  Ulpiani.  Sull'azione  viduttrice  dei 
batteri  dinitrificanti. 

Gazz.  chim.  Ital.,  29,  49. 

Bull.  soc.  chim.,  (3)  24,  363. 

J.  Chem.  Soc.  (London),  76,  IE,  444. 
Studied  the  action  of  the  denitrifying  bacteria  and  found 
that  B.  denitrificans  V.  reduced  beryllium  nitrate  and, 
in  general,  the  more  electro-positive  the  metal  and  the 
lower  its  atomic  weight  the  more  rapidly  doesdenitri- 
fication  take  place. 

1900;  i.  Bruner,  Ludwig.  Ueber  die  Hydrolyse  der  Salz- 
losungen. 

Ztscnr.  phys.  Chem.,  32,  133. 

Chem.  Centrbl.,   1900,  I,  532. 

Bull.  soc.  chim.,  (3)  26,  599. 

Gives  figures  for  the  hydrolysis  of  solutions  of  BeCl2, 
Be(NO3)2,  and  BeSO4,  compared  with  corresponding 
salts  of  iron  and  aluminum.  The  beryllium  salt? 
showed  smaller  degree  of  hydrolysis  than  either  of  the 
others. 
1900;  2.  Nielsen,  R.  A.  Gliihkorper  aus  Beryllerde. 

Danish  patent  No.  4278. 

1900;  3.  Formanek,  J.  Nachweis  der  Metallsalze  mittelst  der 
Absorptionsspectralanalyse  unter  Verwendung  von 
Alkanna. 

Ztschr.  anal.  Chem.,  39,  409. 

If  one  treats  Alkanna  tincture  with  neutral  beryllium 
chloride  or  nitrate,  solution  is  red  violet  and  fluoresces 
strong  orange  red.  The  absorption  spectra  consists  of 
three  distinct  bands  with  position  varying  according  to 
conditions. 

1901;  i.  Hartley,  W.  Noel.  On  the  Quantitative  Spectra  of 
Beryllium. 

Proc.  Roy.  Soc.,  1902,  283-285. 
Chem.  News,  85,  25. 


150  CHEMISTRY  OF   BERYUJUM 

J.  Chem.  Soc.   (London),  82,  237. 

Chem.  Ztg.,  25,  1142. 

Am.  J.  Sci.,  (4)  13,  156. 

Solutions  of  beryllium  salts  of  diminishing  concentra- 
tion examined  spectroscopically  and  the  gradual  extinc- 
tion of  the  several  lines  noted.  Two  lines  A.  3130.3  and 
2478.1  are  still  visible  when  the  concentration  has  fallen 
as  low  as  .00000 1  per  cent. 

1901 ;  2.     Urbain,  G.  and  Lacombe,  H.     Sur  un  nouveau  sel  de 
glucinium  volatile. 

Comptes  rend.,  133,  874. 

Chem.  Centrbl.,  1902,  I,  97. 

J.  Phys.  Chem.,  6,  349. 

Chem.  News,  84,  304. 

Chem.  Ztg.,  25,  1115-. 

J.  Amer.  Chem.  Soc.,  24,  201. 

Ztschr.  anorg.  Chem.,  33,  227. 

Made  Be4O(C2H3O2)6  by  action  of  glacial  acetic  acid 
on  dry  acetate,  excess  of  glacial  acid  being  present. 
Melts  at  283-284,  distills  under  normal  pressure  at 
330-331°  and  its  vapor  can  be  heated  to  360°  without 
decomposition.  Density  of  vapor  determined  at  boiling 
point  of  mercury  13.9.  Not  effected  by  solution  in 
strongest  acetic  acid  even  if  same  is  saturated  with  hy- 
drochloric acid  gas  and  heated  in  closed  tube  to  150°. 
1901 ;  3.  Wells,  H.  L.  Generalizations  on  Double  Halogen 
Salts. 

Amer.  Chem.  Jour.,  26,  390. 

Chem.  Centrbl.,  1901,  II,  1327. 

Includes  2KF.BeF2,   KF.BeF2  and  2KCl.BeCl2  in  his 
list  of  double  halides. 
1901 ;  4.     Friedel,  G.     Sur  un  silicate  de  lithium  crystallize. 

Bull.  soc.  franc,  de  min.,  24,  141. 

Bull.  soc.  chim.,   (3)   25,   1008. 

Chem.  Centrbl.,  1901,  II,  88. 

Sought  to  obtain  some  mixed  crystals  of  L,i2SiO8  and 
Be2SiO4  and  succeeded  in  doing  so.  Claimed  an  ex- 


BIBLIOGRAPHY  OF  BERYLLIUM  151 

ample  of  isomorphism  similar  to  that  between  albite 
and  anorthite. 

1901 ;  5.     Factor.     Ueber  die  Einwendung  des  Natrium  thiosul- 
phate  auf  einige  Metallsalze. 

Chem.  Centrbl.,  1901,  II,  879,  from 

Pharm.  Post,  34,  485. 

J.  Chem.  Soc.   (London),  82,  II,  25. 
Claimed  BeS2O3.nH2O. 

1902;  i.     Wyrouboff,  G.     Sur  quelques  oxalates  de  glucine. 

Bull.  soc.  franc,  de  min.,  25,  71. 

Chem.  Centrbl.,  1902,  II,  631. 

Again  makes  claims  for  the  completely  disproved  theory 
of  trivalent  beryllium.  Made  the  normal  oxalate 
BeC2O4.3H2O  and  gives  crystal  measurements.  Made 
also  double  oxalates  of  beryllium  with  potassium,  rubid- 
ium, sodium  and  lithium. 

1902;  2.     Wyrouboff,  G.     Sur  la  separation  de  la  glucine. 

Bull.  soc.  chim.,  (3)  27,  733. 

Chem.  Centrbl.,  1902,  II,  610. 

J.  Chem.  Soc.   (London),  82,  605.. 

Analyst.,  27,  287. 

Decomposes  beryl  with  KOH,  removes  SiO2,  evapo- 
rates solution  of  chloride  to  small  volume  and  precipi- 
tates beryllium  as  a  double  oxalate  by  means  of 
HKC204. 

1902 ;  3.     Lacombe,  H.     Sur  un  type  de  composes  du  glucinium, 

Comptes  rend.,  134,  772-74. 

Chem.  Centrbl.,  1902,  I,  1087. 

Amer.  J.  Sci.,  (4)   13,  471. 

J.  Chem.  Soc.   (London),  82,  I,  418. 

Chem.  News,  85,  215. 

Chem.  Ztg.,  26,  373. 

Made  the  basic  formate,  acetate,  propionate,  isobuty- 
rate,  butyrate,  and  isovalerianate,  all  of  the  same  type 
as  the  basic  acetate,  viz.,  Be4O(A)6.  All  made  by 
action  of  anhydrous  acid  in  excess  on  the  carbonate 


I52  CHEMISTRY  OF   B^RYLUUM 

and   sublimation   under    diminished   pressure.     All    at- 
tempts to  saturate  and  obtain  the  normal  salt  failed. 
Formate,  insoluble  in  all  solvents. 

Solubility    increases    with    increased   molecular    weight 
of  acid  radicle. 

CONSTANTS. 

M.  P.        B.  P.  760  mm.  B.P.  19  mm. 
Basic  formate,  sublimes  without 
fusion 

Basic  acetate 283-284  330-331  sublimes 

Basic  propionate 119-120  339-341          221 

Basic  isobutyrate 76  336-337          216 

Basic  butyrate liquid  239 

Basic  isovalerianate  liquid  254 

1902;  4.  Weinland,  R.  F.  and  Schlegelmilch.  Ueber  Doppel- 
salze  des  Jodtrichlorids  mit  Chloridin  zweiwertigen 
Metalle. 

Ztschr.   f.   anorg.   Chem.,  30,    140. 

J.  Chem.  Soc.  (London),  82,  315. 
Prepared  2lCl3.BeCl2.8H2O  by  passing  chlorine  into  a 
hydrochloric  acid  solution  of  BeCl2  and  iodine  at  10°. 
Gold  yellow,  very  hydroscopic  needles.  Very  unstable. 
1902 ;  5.  Reubenbauer,  Jacob.  Ueber  die  Loslichkeit  von 
Schwermetallhydraten  in  Natron. 

Ztschr.  anorg.  Chem.,  30,  334. 

J.  Chem.  Soc.  (London),  82,  II,  396. 
Found  that  NaOH  dissolved  Be(OH)2  in  proportion 
to  the  concentration  of  the  NaOH. 

1903;  i.  Freundlich,  H.  Uber  das  Ausfallen  Kolloidaler  Los- 
ungen  durch  Elektrolyte. 

Ztschr.  f.  phys.  Chem.,  44,  129. 

Chem.  Centrbl.,  1903,  II,  232. 

Studied  the  action  of  BeCl2  and  BeSO4  on  colloidal 
As2S8. 

1903;  2.  Vogel,  Fritz.  Untersuchungen  iiber  Nitrite,  (Beryl- 
lium nitrite). 

Ztschr.  anorg.  Chem.,  35,  385. 

Chem.  Centrbl.,  1903,  II,  327. 
Could  not  obtain  a  nitrite  of  beryllium  by  precipitating 


BIBLIOGRAPHY  OF  BERYLLIUM  1*3 

sulphate  with  barium  nitrite.  Precipitate  immediately 
hydrolyzed  and  lost  oxides  of  nitrogen.  His  precipi- 
tated hydroxide  contained  but  a  small  amount  of 
nitrogen  Be  :NO2 :  :i  10.15. 

1903;  3.  Renz,  Carl.  Ueber  Verbindungen  von  Metalhaloiden 
mit  organischen  Basen. 

Ztschr.  anorg.  Chem.,  36,  100-118. 

Chem.  Centrbl.,  1903,  II,  578. 

Succeeded  in  making  but  one  compound  of  beryllium 
with  the  organic  bases,  viz.,  Beryllium  chloride  quin- 
oline,  BeCl2(C9H7N2)2+H2O. 

1903 ;  4.  Renz,  Carl.  Ueber  die  Loslichkeit  der  Hydroxide  des 
Aluminiums,  Berylliums  und  Indiums  in  Ammoniak  und 
Aminbasen. 

Berichte,  36,  2751-55. 

Chem.   Centrbl.,  1903,  II,  823. 

Beryllium  hydroxide  is  quite  insoluble  in  methyl,  ethyl, 
dimethyl  and  diethyl  amine.  This  gives  a  quick  and 
accurate  and  quantitative  separation  from  aluminum.  So- 
lution of  beryllium  and  aluminum  are  dissolved  in  dilute 
nitric  acid,  evaporated  to  remove  acid,  taken  up  in 
water,  shaken  up  with  large  excess  of  ethyl-amine  and 
the  precipitated  beryllium  hydroxide  carefully  washed 
and  aluminum  determined  in  filtrate. 

I9°3>  5-  Van  Oordt,  G.  Verfahren  zur  Reinabscheidung  des 
Berylliums  aus  seinem  Gemenge  mit  Aluminium  und 
Eisen. 

German  Patent  No.  155,466. 

Chem.  Centrbl.,  1904,  II,  1354. 

Separates  the  basic  acetate  by  its  solubility  in  chloro- 
form. 

1904;  i.  Pollok,  James  Holms.  On  the  Extraction  of  Gluci- 
num  from  Beryl. 

Trans.  Royal.  Dublin  Society,   (2)  8,  139-152. 
Extracted  beryl  by  fusion  with  its  own  weight  of  sod- 
ium hydroxide  in  a  salamander  crucible.     After  separat- 
ing silica  from  hydochloric  acid  solution,  he  precipitated 


154  CHEMISTRY  OF  BERYLLIUM 

with  ammonia,  filtered  and  dissolved  the  iron,  aluminum 
and  beryllium  in  hydrochloric  acid  and  saturated  with 
hydrochloric  acid  gas  thereby  separating  the  main  quan- 
tity of  aluminum.  Separated  from  iron  by  ammonium 
carbonate  and  sulphide.  Also  in  other  experiments  sep- 
arated aluminum  as  alum  in  the  ordinary  way.  Made 
perfectly  free  from  aluminum  by  precipitating  same 
with  HKF2  in  dilute  HF  solution.  In  strong  solution 
some  beryllium  is  also  precipitated. 
Basic  carbonate  finds  formula  approximately  BeCO3.- 
2Be(OH)2.2H2O.  Carbonate  is  soluble  to  the  extent 
of  58  grams  in  one  liter  saturated  ammonium  carbonate. 
Sulphate  and  chloride  made  in  the  usual  manner,  gives 
melting  point  of  BeCl2  as  about  400°  and  boiling  point 
at  about  500°.  Made  impure  metallic  beryllium  by 
action  of  Na  on  anhydrous  chloride  in  nickel  crucible. 
Dark  gray  powder.  Could  not  fuse  at  atmospheric 
pressure.  In  atmosphere  of  H  it  volatilized  without 
fusion. 

1904;  2.  Haber,  F.  and  Van  Oordt,  G.  Ueber  Berylliumver- 
bindungen.  I  Mitteilung.  Ueber  Beryllium  Hydrox- 
ide. 

Ztschr.  anorg.  Chem.,  38,  377-398. 

Chem.  Centrbl.,  1904,  I,  858. 

A  study  of  the  hydroxide  of  beryllium  convinced  them 
that  it  existed  in  two  modifications,  first,  when  freshly 
precipitated  which  is  readily  acted  upon  by  reagents 
and  a  second  or  older  form,  produced  by  standing  or 
by  boiling  which  is  much  less  readily  attacked. 

>"  3-     Tanatar,  S.     Studies  upon  the  Valency  and  the  Atomic 
Weight  of  Beryllium. 

J.  Russ.  Phys.  and  Chem.  Soc.,  36,  82-86. 

Chem.  Centrbl.,  1904,  I,  1192. 

Repeats  the  work  of  Urbain  and  Lacombe  (1901 ;  2)  on 
the  acetate  and  comes  to  the  conclusion  that  Be  is  a 
tetravalent  element  with  the  atomic  weight  18.2. 


BIBLIOGRAPHY  OF  BERYLLIUM  155 

1904;  4.  Haber,  F.  and  Van  Oordt.  Berylliumverbindungen. 
II  Mitteilung. 

Ztschr.  anorg.  Chem.,  40,  465-. 

Chem.  Centrbl.,  1904,  II,  688. 

Separates  beryllium   from  aluminum  and  iron  by  the 
solubility  of  its  basic  acetate  in  chloroform. 
1904 ;  5.     Parsons,  Charles  Lathrop.     A  Revision  of  the  Atomic 
Weight  of  Beryllium. 

Jour.  Amer.  Chem.  Soc.,  26,  721. 

Ztschr.  anorg.  Chem.,  40,  400. 

Chem.  News,  90,  61,  75. 

Chem.  Centrbl.,  1904,  II,  820. 

Describes  the  preparation  of  pure  material  including 
the  sulphate,  chloride,  acetyl-acetonate  and  basic  ace- 
tate. States  that  the  supposed  new  element  noted  by 
Kriiss  and  Moraht  in  beryllium  compounds  is  a  mixture 
of  zinc  and  iron.  Gives  properties  of  the  chloride,  sul- 
phate, acetyl-acetonate  and  basic  acetate.  By  the  analy- 
sis of  seven  samples  of  beryllium  acetyl-acetonate  and 
nine  of  basic  acetate,  obtained  the  atomic  weight  9.113. 
Results  on  sulphate  unsatisfactory  and  the  method  un- 
reliable in  the  opinion  of  the  author. 

1904;  6.  Neisch,  A.  C.  A  New  Separation  of  Thorium  from 
Cerium,  Lanthanum  and  Didymium  by  Meta-nitroben- 
zoic  acid. 

J.  Amer.  Chem.  Soc.,  26,  781. 

Chem.  Centrbl.,  1904,  II,  848. 

Meta  nitrobenzoic  acid  does  not  precipitate  beryllium. 
1904 ;  7.     Myers,  Ralph  E.     Results  obtained  in  Electrochemical 
Analysis  by  the  Use  of  a  Mercury  Cathode. 

J.  Amer.  Chem.  Soc.,  26,  1124. 

Chem  Centrbl.,  1904,  II,  1338. 

Separation  of  beryllium  from  chromium  and  iron.  By 
the  use  of  a  mercury  cathode  all  the  iron  and  chromium 
present  in  a  slightly  acid  solution  of  the  sulphates  and 
beryllium  sulphate  can  be  deposited  in  the  mercury,  leav- 
ing pure  beryllium  sulphate  behind. 


156  CHEMISTRY  OF  BERYLLIUM 

1904;  8.  Wetherel,  E.  W.  An  Attempt  to  Explain  the  Irregu- 
larities of  the  Atomic  Weights  of  Beryllium,  Argon 
and  Tellurium. 

Chem.  News,  90,  260. 
Chem.  Centrbl.,  1905,  I,  7. 

1904;  9.  Pollok,  James  Holms.  The  Heat  of  Formation  of 
Glucinium  Chloride. 

J.  Chem.  Soc.  (London),  85,  603. 

Pro.    Chem.    Soc.    (London),    20,    61. 

Chem.  Centrbl.,  1904,  I,  1243,  1593. 
Describes  the  extraction  of  the  oxide  from  beryl.     For- 
mation  and   properties   of   anhydrous   chloride.     Melt- 
ing point  of  chloride  about  400°. 
Molecular  heat  of  solution  BeCl2=44.5  K°, 
Molecular  heat  of  solution  BeSO44H2O=o.85  K°, 
Molecular  heat  of  formation  BeCl2=i55  K°. 
Prepared   metallic   beryllium   by   action   of   sodium   on 
chloride  and  obtained  an  impure  product.     Says  metal 
volatilizes  without  fusion  at  ordinary  pressure. 

1904;  10.  Parsons,  Charles  Lathrop.  Equilibrium  in  the  Sys- 
tem Beryllium  Oxide,  Sulphuric  Anhydride  and  Water. 

J.  Amer.  Chem.  Soc.,  26,  1433. 

Ztschr.  anorg.  Chem.,  .42,  250. 

Chem.  Centrbl.,  1905,  I,  2. 

Made  a  study  of  the  various  published  sulphates  of 
beryllium  including  the  so-called  basic  sulphates  and 
concludes  that  the  only  definite  sulphates  are  the  tetra- 
hydrate  and  dihydrate,  and  by  the  application  of  phase 
rule  considerations,  the  basic  sulphates  are  shown  to  be 
either  the  hydroxide  or  a  solid  solution  of  the  sulphate 
in  the  hydroxide. 

1904;  ii.  Parsons,  Charles  Lathrop.  "Beryllium"  or  "Glu- 
cinium" Science,  Dec.  9,  1904. 

Chem.  News,  91,  75. 

Discussion  of  the  proper  name  for  element.  Prefers 
beryllium. 


BIBLIOGRAPHY  OF  BERYLLIUM  157 

1904;   12.     Pollok,  James   Holms.     The   Composition  of  Beryl. 

Proc.  Chem.  Soc.   (London),  20,  189. 

J.  Chem.  Soc.   (London),  85,  1630-37. 

Chem.  Centrbl.,  1905,  I,  556. 

By  fractional  sublimation  of  the  chloride  of  beryllium, 
he  obtained  chlorides  which  on  analysis  yield  equiva- 
lents for  Be  all  the  way  from  4.77-18.74  and  concluded 
the  beryllium  is  really  a  mixture  of  two  elements. 
Examined  the  oxides  from  the  two  chlorides  spectro- 
scopically. 
1905;  I.     Howe,  James  Lewis.     "Glucinium"  or  "Beryllium." 

Science,   Feb.    17,    1905. 

Chem.  News,  91,  123. 
Reply  to   1904;   10,  Prefers  glucinium. 

1905;  2.     Parsons,     Charles    Lathrop.     "Beryllium"     or     "Glu- 
cinium." 

Science,  Jan.  6,  1905. 

Chem.  News,  91,  123. 

Chem.  Centrbl.,  1905,  I,   1129. 
Reply  to  Howe  1905 ;  i. 

1905 ;  4.     Parsons,  Charles  Lathrop.     On    the    Complexity    of 
Beryllium. 

J.  Amer.  Chem.  Soc.,  27,  233. 

Chem.  News,  91,  92. 

Chem.  Centrbl.,  1905,  I,  995,  1306. 
Discusses  the  work  of  Pollok  (1905,  4)  and  claims  that 
his  results  are  easily  explained  by  the  action  of  water 
on   beryllium   chloride   and   that   sufficient   precautions 
were  not  taken  to  guard  against  its  presence. 
1905;  5.     Parsons,    Charles    Lathrop.      Note    on    the    Atomic 
Weight  of  Carbon  and  Beryllium. 

J.  Amer.  Chem.  Soc.,  27,  1204. 

Ztschr.  anorg.  Chem.,  46,  215. 

Chem.  Centrbl.,  1905,  II,  956,  1155. 
Obtains    new    figures    from  his    previously    published 
analyse   for  the   atomic   weight   of  beryllium.     By   an 
algebraic  calculation  both  the  atomic  weight  of  carbon 


158  CHEMISTRY  OF  BERYUJUM 

and    beryllium   are    independently   obtained    from   the 
previously  published  figures. 
Atomic  weight  Be=  9.112. 
Atomic  weight  C  =12.007. 

1905 ;  6.  Kahlbaum,  G.  W.  A.  and  Sturm,  E.  Ueber  die  Ver- 
andlichkeit  des  Spezifischen  Gewichtes. 

Ztschr.  anorg  Chem.,  46,  237. 

Chem.  Centrbl.,  1905,  II,  1068. 

Compares   beryllium    to   other   members   of   the    same 
group  and  gives  reasons  why  it  was  not  used  in  his 
research. 
1905 ;  7.     Levi-Malvano,  Mario.  Gli  idrati  del  solfato  di  berillio. 

Atti.  R.  Accad.  die  Lincei,  Roma,  (5)  14,  II,  502-10. 

Ztschr.  anorg.  Chem.,  48,  446. 

Chem.  Centrbl.,  1906,  I,  321,  1223. 
Describes  a  sulphate  hexahydrate  of  beryllium  which 
he  makes  from  supersaturated  solution  and  states  that 
it  yields  a  blue  oxide  on  ignition.  Gives  solubility  curves 
of  the  hexahydrate  and  also  the  tetrahydrate.  Con- 
cludes that  a  sulphate  monohydrate  and  anhydrous  sul- 
phate both  exist. 

1906;  I.  Parsons,  Charles  L.  and  Robinson,  W.  O.  Equili- 
brium in  the  System  Beryllium  Oxide,  Oxalic  Anhy- 
dride and  Water. 

J.  Amer.  Chem.  Soc.,  28,  555. 

Ztschr.  anorg.  Chem.,  49,  178. 

Chem.  Centrbl.,  1906,  II,  8. 

Made  a  study  of  the  oxalates  of  beryllium  in  the  same 
manner  as  the  previous  work,  (1904,  10)  on  the  sul- 
phate and  concludes  that  an  acid  oxalate  does  not 
exist  and  the  oxalates  of  beryllium  alone  are  the  mono 
and  trihydrates.  Further  that  all  of  the  so-called  basic 
oxalates  are  in  reality  solid  solutions  approaching  the 
hydroxide  in  composition.  Give  a  list  and  general 
discussion  of  basic  beryllium  compounds  and  state  their 
belief  that  no  definite  basic  compounds  claimed  to  have 
been  formed  in  presence  of  water  have  any  real  exist- 


BIBLIOGRAPHY  OF  BERYUJUM  159 

ence  as  chemical  compounds.  Cut  and  drawing  of 
crystals  of  the  trihydrated  oxalate.  Purification  of 
material  by  recrystallization  of  the  basic  acetate  from 
glacial  acetic  acid. 

1906;  2.     Parsons,  Charles  L.  and  Barnes,  Stuart  K.     The  Sep- 
aration and  Estimation  of  Beryllium. 

Science,  24,  240. 

J.  Amer.  Chem.  Soc.,  28,  1589. 

Chem.  Centrbl,  1907,  I,  67. 

Ztschr.  f.  anal.  Chem.,  46,  292. 

Chem.  Centrbl.,  1907,  II,  96. 

J..  Chem.  Soc.,  92,  52. 

Chemical  Abstracts,  i,  27. 

Beryllium  is  separated  from  aluminum  and  iron  by  the 
complete  solubility  of  its  hydroxide  in  a  hot  saturated 
solution  of  acid  sodium  carbonate — ferric  hydroxide  and 
aluminum  hydroxide  being  completely  insoluble.  Dou- 
ble precipitation  is  essential.  Beryllium  hydroxide  must 
be  washed  with  water  containing  an  electrolyte  in  so- 
lution, for  when  pure  it  rapidly  washes  through  the 
filter  in  a  colloidal  condition. 

1906;  3.     Parsons,  Charles  L,  and  Robinson,  W.  O.     The  Basic 
Solutions  of  Beryllium  Sulphate. 

Science,  24,  202. 

Freezing-point  determinations,  on  both  dilute  and  con- 
centrated solutions,  show  that,  per  mol  of  SO3,  any 
increase  in  basic  ratio  over  the  normal  salt  raises  the 
freezing-point.  The  osmotic  effect  of  the  sulphate  is, 
therefore,  always  decreased  by  dissolving  in  it  its  own 
hydroxide.  The  electrical  conductivity  of  the  basic 
solutions  is  less  than  that  of  normal  solutions  contain- 
ing the  same  amount  of  SO3.  Migration  experiments 
show  that  beryllium  forms  no  part  of  the  anion.  The 
basic  solutions  are  not  precipitated  by  crystalloids;  but 
on  dialysis  hydroxide  is  left  on  the  membrane,  and  the 
dialyzed  solution  has  a  lower  basic  ratio. 


l6o  CHEMISTRY  OF  BERYLLIUM 

1906;  4.  Parsons,  Charles  L.  and  Roberts  Edwin  J.  Beryllium 
Carbonate. 

Science,  24,  39. 

Normal  beryllium  carbonate  can  not  be  made  at  ordi- 
nary pressures  in  contact  with  water.  BeCO4-f-4H2O 
described  by  Klatzo  does  not  exist,  and  attempts  to 
make  it  by  his  method  yield  only  slightly  carbonated  hy- 
droxide. Basic  beryllium  carbonate  appears  to  have  no 
definite  composition  and  can  be  almost  completely  con- 
verted into  the  hydroxide  by  boiling  in  water.  All  at- 
tempts to  increase  the  proportion  of  the  CCX  components 
over  the  proportion  2Be(OH)2.BeCO3  failed,  although 
CO2  was  passed  for  three  months  through  the  basic  car- 
bonate under  slightly  increased  pressure.  The  basic  car- 
bonates described  in  literature  must  have  contained  at 
least  one  or  two  per  cent,  of  the  carbonate  used  as  a 
solvent  or  precipitant. 

1906;  5.  Parsons,  Charles  L.  and  Fuller,  Carl  T.  Further 
Study  of  the  Sulphates  of  Beryllium. 

Science,  24,  202. 

Crystals  were  obtained  from  solutions  with  a  ratio  as 
high  as  3BeO/2SO3.  These  crystals  are  in  every  case 
the  normal  tetrahydrate,  and  by  their  separation  the 
mother-liquors  are  rendered  more  basic.  Repeated  at- 
tempts to  obtain  the  hexa-hydrate  described  by  Levi- 
Malvano  (Ztschr.  anorg.  Chemic,  48,  446,)  have  re- 
•  suited  in  failure.  Although  the  conditions  described 
by  that  author  were  faithfully  followed  and  other  meth- 
ods used,  the  tetrahydrate  invariably  separated. 

1906;  6.  Van  Oordt,  G.  Verfahren  Zur  Uberfiihrung  von 
Beryllium  Hydroxide  in  einen  nicht  nur  fur  Alkali, 
sondern  auch  fur  Saure  schwerloslichen  bejw.  unlos- 
lichen  Zustand. 

Kl.  Patent,  I2tn.  No.  165,488  of  Sept.  12,  1903. 

Chem.  Centrbl.,  1906,  I,  108. 
A  patent  on  the  principle  published  by  Haber  and  Van 


BIBLIOGRAPHY  OF  BERYLLIUM  l6l 

Oordt  (1904;  2)  which  he  claims  to  apply  to  a  method 
of  separation. 

1906;  7.  Brail,  F.  and  Van  Oordt,  G.  Verfahren  Zur  Tren- 
nung  der  Beryllerde  von  Thonerde  und  eventuell  Eisen. 

Kl.  Patent,  I2m.  No.  175,452. 

Chern.  Centrbl.,  1906,  II,  1370. 

Chemical  Abstracts,  I,  2316,  2514. 

A  patent  for  the  separation  of  beryllium  on  the  princi- 
ple described  in  1906;  2. 

1906;  8.  Glassmann,  B.  Zur  quantitativen  Trennung  des 
Beryllium  von  Aluminium. 

Berichte,  39,  3366-67. 

Chem.  Centrbl.,  1906,  II,  1584. 

Chem.  Abs.,  i,  151. 

Claims  to  separate  by  essentially  the  same  method  as 
proposed  by  Berthier  (1843;  2)  and  discarded  as  early 
as  1844  0844;  i)  by  Bottinger. 

1906;  9.  Glassmann,  B.  Zur  quantitativen  Bestimmung  des 
Berylliums. 

Berichte,  39,  3368-69. 

Chem.  Centrbl.,   1906,  II,   1584. 

Chem.  Abs.,  i,  152. 

Precipitates  beryllium  hydroxide  from  neutral  solution 
of  pure  salts  by  a  mixture  of  potassium  iodide  and 
iodate  after  previous  removal  of  iron  and  alumina.  Has 
the  advantage  over  NH4OH  that  the  precipitate  is 
easily  washed. 

1906  ;  10.  Tanatar,  S.  Uber  die  Wertigkeit  und  das  Atom- 
gewichte  des  Berylliums  (Spezifische  Warme  des  Beryl- 
liums oxyds). 

Jour.  Russ.  Phys.  Chem.  Ges.,  38,  850-54. 

Chem.  Centrbl,  1906,  II,   1807. 

Determines  the  specific  heat  of  the  oxide  at  100-117° 
as  .2898  and  calculates  therefrom  an  abnormally  low 
specific  heat  for  the  metal,  and  argues  therefrom  for  the 
tetravalency  of  the  element  exactly  as  the  well  known 
ii 


l62  CHEMISTRY  OF  BERYIJJUM 

low  specific  heat  of  the  element  was  formerly  used  as 
an  argument  for  its  trivalency. 

1906;  ii.       Olmstead,    Charles   M.     Die   Bandenspektren   nahe 
verwandte  Verbindungen. 

Zeit.     f.  wiss.     Photographic,  Photophysic  u.  Photo- 

chemie,  4,  255-91. 
Chem.  Centrbl.,  1907,  I,  147. 

Studied  the  band  spectra  of  Ba,  Sr,  Ca  and  Mg.  Could 
obtain  no  spectrum  from  beryllium  chloride  and  thinks 
temperature  was  probably  not  high  enough  for  this  pur- 
pose. 

1906;  12.     Friedheim,    Carl.     Zur   quantitativen   Trennung   des 
Berylliums  und  Aluminiums. 

Berichte,  39,  3868-69. 

Chem.  Centrbl.,  1907,  I,  191. 

Chem.  Abs.,  I,  277. 

Calls  attention  to  the  fact  that  Glassmann's  (1906;  8) 
supposed  new  method  had  been  proposed  much  earlier 
and  tried  by  several  authors. 

1906;  13.     Parsons,  Charles  L.     Beryllium  Nitrate. 

Science,  25,  402. 

Prepares  Be(NO3)2.4H2O  by  crystallizing  from  strong 
nitric  acid.  Crystals  very  deliquescent,  lose  their  N2O5 
easily,  are  stable  only  in  strong  nitric  acid  or  in  air 
saturated  with  its  vapor,  melt  in  their  own  water  of 
crystallization  at  60.5,  soluble  in  alcohol  and  in  acetone. 

1907  ;   i.     Glassmann,  B.     tJber  die  Konstitution  der  fettsauren 
Salze  des  Berylliums  und  sur  Wertigkeit  des  letztern. 

Chem.  Ztg.,  31,  8-9. 

Chem.  Centrbl.,  1907,  I,  707. 

J.  Chem.  Soc.,  92,  109. 

Chem.  Abs.,  i,  701. 

Criticises  the  conclusions  of  Tanatar  (1904;  3)  that  the 
basic  beryllium  salts  of  the  fatty  acid  series  show  beryl- 
lium to  be  tetravalent.  Explains  valency  on  divalency 
basis. 


BIBLIOGRAPHY  OF  BERYUJUM  163 

1907;  2.     Kiihne,    K.    A.     Verfahren      zur      Darstellung     von 
Metallen,  u.  s.  w. 

Patent  Kl  4oa,  No.  179,403. 

Chem.  Centrbl.,  1907,  I,  1474. 

Proposes  to  separate  Be,  Bo,  Si,  etc.,  by  Goldschmidt's 
aluminum  method  by  adding  them  to  the  mixture  in  the 
form  of  chlorates  or  perchlorates. 
1907 ;  3.     Parsons,  Charles  L.     The  Vagaries  of  Beryllium. 

Science,  26,  569-74. 

Chem.  News,  96,  131. 

Address  of  the  chairman  of  the  Inorganic  Section,  To- 
ronto meeting,  American  Chemical  Society. 
1907 ;  4.     Glassmann,  B.     Zur  Kentniss  der  Chromate  des  Beryl- 
liums. 

Berichte,  40,  2602-4. 

Chem.  Centrbl.,  1907,  II,  375. 

Chem.  Abs.,  I,  2352. 

Claims  to  have  made  neutral  chromate,  BeCrO4.H2O  by 
"neutralizing"  a  concentrated  water  solution  of  chromic 
acid  with  basic  beryllium  carbonate  and  evaporating. 
Obtained  reddish  yellow  monoclinic  crystals  which  are 
decomposed  by  water  with  separation  of  a  basic  chro- 
mate, to  which  he  gives  the  formula,  BeCrO4.6Be(OH), 
or  by  precipitation  of  ammonium  chromate  with  BeSO4 
solution. 

(Other   investigators   who   have   tried   to   produce  the 
chromate  in  this  manner  have  obtained  only  indefinite 
basic  mixtures.) 
I9°7  ;  5     Steinmetz,  Hermann.     Uber  Beryllium  Acetate. 

Ztschr.  f.  anorg.  Chem.,  54,  217-22. 

Chem.  Centrbl.,  1907,  II,  528. 

J.  Chem.  Soc.,  92,  673. 

Chem.  Abs.,  I,  2672. 

Basic  beryllium  acetate  gives  octahedral  crystals,  from 
organic  solvents  which  on  sublimation  yield  doubly  re- 
fracting leaves  and  prisms.  It  forms  an  unstable  com- 
pound, Be4O(Ac)6.3C3H5N  in  cold  pyridine.  He  made 


164  CHEMISTRY  OF 

normal  beryllium  acetate,  Be(C2H3O2)2  for  the  first  time 
by  heating  equal  parts  of  basic  acetate  and  glacial  acetic 
acid  with  5-6  parts  acetic  anhydride  for  2  hours  in  a 
sealed  tube  at  140°.  It  forms  double  refracting  small 
leaflets  which  are  insoluble  in  water,  alcohol,  ether  and 
organic  solvents.  They  are  hydrolyzed  by  continued 
boiling  in  water,  melt  with  decomposition  at  300°  and 
yielding  a  sublimate  of  the  basic  acetate. 

1907;  6.     Glassmann,  B.     Ein  Beitrage  zur  Bivalenz  des  Beryl- 
liums.    Das  Berylliumpikrat. 

Berichte,  40,  3059-60. 

Chem.  Centrbl.,  1907,  II,  777. 

J.  Chem.  Soc.,  92,  695. 

Chem.  Abs.,  i,  2539. 

By  "neutralizing"  a  water  solution  of  picric  acid  with 
basic  beryllium  carbonate,  obtained  a  substance 
in  yellow  scales  to  which  he  gave  the  formulas 
Be(C6H2O7N3)2.3H2O  by  calculation  from  its  BeO 
content.  By  treating  with  ether  he  states  it  loses  one 
molecule  of  water.  On  drying  all  the  water  is  removed 
and  the  residue  was  soluble  in  alcohol,  acetone,  and  py- 
ridine  but  difficultly  soluble  in  ether.  In  acetophenon 
it  gave  a  freezing  point  lowering  giving  a  molecular 
weight  of  465.  By  the  action  of  water  it  is  hydrolyzed 
and  yields  a  basic  mass  to  which  Glassmaun  gives  the 
formula  Be(C6H2O7N3)2.2oBe(OH)2. 

1907;  7.     Bourion,  F.     Action  du  chlor  et  du  chlorur  de  soufre 
sur  quelques  oxydes. 

Comptes  rend.,  145,  62-64. 

Chem.  Centrbl.,  1907,  II,  880. 

Chem.  Abs.,  I,  2988. 

Beryllium  oxide  is  converted  into  BeCl2  by  the  action 
of  a  stream  of  Cl  and  S2C12  at  a  red  heat. 
1907;  8.     Nicolardot,  P.     Glucinium  ou  Beryllium. 

Bull.  soc.  chim.,  (4)  I,  675-81. 

Chem.  Centrbl.,  1907,  II,  1152. 
Argues  in  favor  of  the  French  usage. 


BIBLIOGRAPHY  OF  BERYLUUM  165 

1907;  9.     Stein,  Gerh.     Uber  die  Darstellung  einger  Silicate. 

Ztschr.  f.  anorg.  Chem.,  55,  159-74. 

Chem.  Centrbl.,  1907,  II,  1218. 

Obtained  a  meta  silicate  BeSiO3  with  a  density  2.35  and 
an  orthosilicate  with  density  2.46  by  fusing  the  oxide 
with  SiO2  in  a  carbon  tube  oven  electrically  heated  to 
above  2000°.  Melting  point  of  each  about  2000°. 
1907;  10.  Parsons,  C.  L.,  Robinson,  W.  O.  and  Fuller,  C.  T. 
The  Soluble  Basic  Sulphates  of  Beryllium. 

Journal  of  Physical  Chemistry,  n,  655. 

Chem.  Centrbl.,  1908,  I. 

J.  Chem.  Soc.,  94,  105. 

It  is  shown  that  a  solution  of  beryllium  hydroxide  in  a 
solution  of  beryllium  sulphate  raises  the  freezing  point 
of  the  latter  and  lowers  its  conductivity.  The  solutions 
obtained  are  not  colloidal  nor  does  the  beryllium  enter 
into  a  complex  anion  as  is  shown  to  be  the  case  when 
a  berylonate  is  present. 
1907;  ii.  Parsons,  Charles  L.  Solution  in  a  Dissolved  Solid. 

Jour,  of  Phys.  Chem.,  n,  660. 

Chem.  Centrbl.,  1908,  I. 

J.  Chem.  Soc.,  94,  89. 

An  explanation  presented  with  several  analogous  ex- 
periments to  account  for  the  solubility  of  Be(OH)2  in 
solutions  of  beryllium  salts. 

1907  ;   12.     Tanatar,  S.  and  Kurowski,  E.  K.     Uber  einige  Salze 
des  Berylliums  und  Zirkoniums. 

J.  Russ.  Phys.  Chem.  Soc.,  39,  936-43. 

Chem.  Centrbl.,  1908,  I,  102. 

J.  Chem.  Soc.,  92,  888. 

Adhering  to  his  previously  announced  belief  in  the 
tetravalency  of  beryllium,  he  claims  to  have  made  salts 
of  several  organic  acids  by  saturating  their  water  solu- 
tions with  basic  beryllium  carbonate.  By  evaporating 
these  solutions  and  analyzing  the  solid  obtained  for  BeO 
only,  he  calculates  the  formulas  given  below.  Formate, 
Be(CHO2)2,  Basic  Formate,  Be4O(CHO2)«. 


l66  CHEMISTRY  OF  BERYLUUM 

Crotonate,  Be4O(C4H15O2)0,  soluble  in  benzene  and  al- 
cohol, crystals,    volatile    with    decomposition.       Gives 
normal  molecular  weight  in  benzene. 
Isocrotonate,  much  the  same  as  the  crotonate. 
Laevulinate,  Be4O(C5H7O3)6,  soluble  in  water,  alcohol 
and  benzene  and  freezing  point  in  benzene  corresponds 
to  above. 

Succinate,  Be4O(C4H4O4)3,  white  powder  insoluble  in 
benzene  and  alcohol. 
Maleate  and  Fumarate,  BeC4H2O4. 
Citraconate,  BeC5H4O4. 

Also  obtained  derivatives  of  the  basic  butyrate  and  pro- 
prionate  as  follows  by  treating  them  with  acetyl 
chloride, 

Be4O(C4H7O2)4.(C2H3O2)2,  melting  point  15°,  boiling 
point  351°,  soluble  in  benzene  and  ether. 
Be40(C4H502)3.(C2H302)3,   melting  point    127°,   boil- 
point  330°  without  decomposition.     Soluble  in  benzene 
and  ether. 

(Note.  While  the  acetyl  derivatives  of  the  well  known 
butyrate  and  proprionate  can  probably  be  depended 
upon,  the  salts  enumerated  above  need  confirmation  as 
it  i?  a  perfectly  simple  matter  to  get  residues  of  this  char- 
acter with  organic  acids  which  will  calculate  almost  any 
formula  if  their  content  of  beryllium  oxide  is  the  only 
criterion.  It  should  also  be  remembered  that  the  ad- 
dition of  basic  beryllium  carbonate  to  any  organic  acid 
beyond  the  amount  necessary  to  form  the  normal  salt 
causes  solutions  of  the  substance  formed  to  have  a 
higher  freezing  point  than  the  solution  of  the  normal 
salt,  which  might  easily  account  for  the  molecular 
weights  calculated  within  the  limits  of  error  of  Tanatar's 
experiments.  Certainly  neither  the  normal  formate  nor 
the  basic  formate  of  Lacombe  can  be  prepared  in  the 
presence  of  water,  and  many  attempts  at  preparing 
the  succinates  by  the  compiler  of  this  bibliography  have 
resulted  only  in  indefinite  mixtures  of  variable  com- 


BIBLIOGRAPHY  OF  BERYLLIUM  167 

position,  one  of  which  could  easily  have  been  found  to 
meet  the  description  of  Tanatar's  succinate  and  still 
have  been  simply  a  solid  solution.) 

1907;  13.  Tanatar,  S.  M.  and  Kurowski,  E.  K.  Beryllium 
and  Zirconium  Benzoates. 

J.  Russ.   Phys.  Chem.   Soc.,   1907,  39,   1630. 

J.  Chem.  Soc.  (London),  94,  166. 

By  action  of  water  solution  of  sodium  benzoate  on  a 
solution  of  beryllium  acetate,  he  obtained  a  white 
amorphous  substance,  soluble  in  benzene  and  acetone 
which  from  its  BeO  content  he  assumes  to  be  a  ben- 
zoate of  type  Be4O(Ac)6  and  claims  it  is  similar  to  a 
zirconium  benzoate,  similarly  obtained  as  a  further  ar- 
gument for  the  tetravalency  of  beryllium. 

1907;  14.  Raikow,  P.  Weitere  Untersuchungen  iiber  die  Ein- 
wirkung  der  Kohlensaure  auf  die  Hydrate  der  Metalle. 

Chem  Ztg.,  31,  55,  87.  " 

Chem.  Centrbl.,  1907,  I,  695. 

Chem.  Abstracts,  i,  825,  967. 

Beryllium  forms  no  carbonate  unless  possibly  a  basic 
carbonate  of  composition  BeCO3.3Be(OH)2. 
1907;   15.     Biltz,  W.  and  Zimmermann,   Fr.       Ueber  die  Ein- 
wirkung  von  Silbernitrat  and  Mercurinitrat  auf  einige 
Anorganische  Hydroxide. 

Berichte,  40,  4979-84. 

Chem.  Centrbl.,  1908,  I,  444. 

Silver  nitrate  is  without  effect  on  beryllium  hydroxide. 
Mercuric  nitrate  solution  is  colored  yellowish  red  by 
the  neutral  hydroxide.  Authors  conclude  from  com- 
parison that  Be  (OH)  2  has  an  ion  solubility  of  the  high 
order  of  io~5. 

1908;  i.  Glassmann,  B.  Zur  Konstitution  der  fettsauren 
Salze  des  Berylliums,  iiber  einige  Neue  Beryllium 
orthosalze  und  iiber  Salze  organische  Orthosauren 
anderer  Elements. 

Berichte,  41,  33. 
Argues    for    his    constitutional    formulas    for    organic 


l68  CHEMISTRY  OF  BERYLLIUM 

beryllium  compounds  as  against  Tanatar.  Also  offers 
the  following  new  salts  all  of  which  need  confirmation 
by  equilibrium  experiments  before  being  accepted  (See 
note  1907;  13): 

Lactate,  Be2O(C3H5O3)2.H2O,  crystals,  soluble  in 
water ; 

Glycolate,  Be2O(C2H3O3)2.H2O,  crystals,  soluble  in 
water ; 

Trichloracetate,  Be,O(C2Cl3O2)2,  glassy  mass; 
Ethylglycolate,  Be2O(C2H5.C2H2O3)2.H2O ; 
Phenylglycolate,  Be2O(C6H5.C2H2O3)2 ; 
Chloroproprionate,  Be2O(C3H4ClO2)2.H2O ; 
Salicylate,  Be2O(C7H5O8)2 ; 
Cyanacetate,  Be4O(C2H2  CNO2)fl,  glassy  mass. 
Dichloracetate,  Be4O(C2HCl2O2)6,  crystalline; 
Monobromacetate,  Be4O(C2H2BrO2)c,  crystalline. 
Monochloracetate,    Be4O(C2H2ClO2)6,   crystalline. 
Monobromproprionate,  Be4O(C3H4BrO2)6,  crystalline. 
All  the  above  "salts"  are  easily  soluble  in  water,  in- 
soluble in  benzene  and  chloroform  and  all  non-volatile. 
All  were  made  by  "neutralizing"  the  water  solution  of 
the  acid  with  basic  beryllium  carbonate  and  evaporat- 
ing.    The    composition   of   the    solid    residue    was    in- 
ferred from  the  content  of  BeO  found,  adding  water 
of  crystallization   where  necessary  to  make  the  calcu- 
lated quantity  of  oxide  agree  therewith. 

1908;  2.  Noyes,  A.  A.,  Bray,  W.  C.  and  Spear,  E.  B.  A  Sys- 
tem of  Qualitative  Analysis  for  the  Common  Elements. 
Part  III  Analysis  of  the  Aluminium  and  Iron  Groups 
including  Beryllium,  Uranium,  Vanadium,  Titanium. 
Zirconium  and  Thallium. 
J.  Amer.  Chem.  Soc.,  30,  481 

1908;  3.  Cameron,  F.  K.  and  Robinson,  W.  O.  The  Action  of 
Carbon  Dioxide  under  Pressure  upon  a  Few  Metal 
Hydroxides  at  o°C. 

Jour.  Phys.  Chem.,  12,  562. 

The  authors  show  that  no  definite  carbonate  of  beryllium 
exists. 


INDEX  OF  AUTHORS. 


Ampola,  G.,  1899,    14. 
Atkinson,  E.  A.,  1895,    9. 
Atterberg,  Albert,  1873,  7,  8  ;  1874, 

i  ;  1875,  4. 

Austin,  Martha,  1899,  8,  9. 
v.  Awdejew,  1842,  2. 

Balard,  A.  G.,  1834,   i. 

Becquerel,  A.  C.,  1831,  2. 

Behrens,  H.,  1891,  2. 

Berthier,  Pierre,  1843,  2. 

Berthemot,  1831,  i. 

Berzelius,  J.  J.,    1815,  i  ;    1823,    i  ; 

1825,   i  ;    1826,  i,  2;    1831,  3; 

1833,  2  ;  1834,  2. 
Blake,  James,  1882,   i. 
Bilitz,  W.,  1907,   15. 
Biot,  Jean  Baptiste,  1838,  i. 
de  Boisbaudran,  Lecoq,  1882,  3. 
Bondard,  O,  1898,  10. 
v.  Bonsdorff,  P.  A.,  1828,  4. 
Borchers,  W.,  1894,  4  ;  1895,  n. 
Bottinger,  Heinrich,  1844,  i. 
Bourion,  F.,  1907,  7. 
Brauner,  B.,  1878,  6  ;  1881,  i. 
Braw,  Frederick,  1906,  7. 
Bray,  W.  C.,  1908,  2. 
Brogger,  W.  C.,  1884,  4. 
Brunner,  Ludwig,  1900,   i. 
Bunsen,  R.  W.,  1875,  i. 
Burgass,  Rob,  1896,  7. 
Bussy,  Antoine  Alexandre,  1828,  3. 
Cahours,  A.,  1860,  i  ;  1873,   I- 
Cameron,  Frank  K.,  1908,  3. 
Carlton-Williams,  W.,  1880,  i. 
Carnelley,  T.,   1879,    i  ;      1880,    i  ; 

1884,  9,  10. 
Caron,  H.,   1858,  3. 
Clarke,  F.  W.,  1883,  4. 
Classen,  A.,   1881,  3. 


Chabrie,  C.,  1886,  5. 

Christiansen,  C.,  1873,  9- 

Ciamician,  G.  L.,  1880,  5. 

Combes,  Alph,  1894,  6. 

Cooke,  J.  P.,  1886,  6. 

Cossa,  A.,  1877,  2. 

Crookes,  W.,  1881,  4;    1887,  3. 

Curtius,  Th.,  1898,  12. 

Damour,  A.,  1843,  3- 

Dana,  E.  S.,  1889,  2. 

Davy,  Humphrey,  1809,  i. 

Debray,  Henri,    1854,  2  ;    1855,  i  ; 

1867,  i. 

Delafontaine,  M.,  1865,  i. 
Deville,  St.  Claire,  1858,  3. 
Donath,  Ed.,  1883,  3. 
Duboin,  A.,  1896,  5. 
Du  Menil,  1823,  2. 
Ebel,  Fr.,  1887,  2. 
Ebelmen,  J.  J.,  1851,  i,  2,  3. 
Elten,  M.,  1893,  4- 
Ekeberg,  A.  G.,  1802,  i. 
Faktor,  F.,  1901,  5. 
Flink,  G.,  1884,  4. 
Florence,  W.,  1898,  13. 
Formanek,  J.,  1900,  3. 
Franck,  L.,  1898,  20. 
Frankland,  E.,  1861,  i. 
Fremy,  E.,  1853,  i. 
Freundlich,  H.,  1903,  i. 
Friedel,  Ch.,  1892,  7. 
Friedel,  G.,  1901,  4. 
Friedheim,  Carl,  1906,  12. 
Fuller,  C.  T.,  1907,  10. 
Gay-Lussac,  L,.  J.,  1811,  i. 
Genth,  F.  A.,  1884,  6. 
Gibbs,  Walcott,  1864,  2,  3,  4. 
Gibson,  John,  1893,  3. 
Gladstone,  J.  H.,  1896,  n;  1897,  6. 


INDEX   OF   AUTHORS 


Glaser,  Charles,  1890,  8. 
Glassmann,  B.,  1906,  8,  9;  1907,  i, 

4,  6  ;  1908,  i. 

Gmelin,  L.,  1801,  i  ;  1840,  i. 
Goldschmidt,  H.,  1898,  14. 
de  Gramont,  H.,  1898,  11. 
Grandeau,  H.,  1886,  2. 
Gratzel  v.  Gratz.  A.,  1892,  3. 
Haber,    F.,   and   Van    Oordt,    G., 

1904,  2,4. 

Harper,  D.  N.,  1886,  4. 
Hart,  Edward,  1895,  6. 
Hartley,  W.  N.,  1883,  5  ;  1884,  5  ; 

1901,  i. 

Haushofer,  K.,  1883,  6. 
Hautefeuille,  P.,  1888,  4,  5  ;  1890, 

9,  10,  14;    1893,  i. 
Havens,  F.  S.,  1897,  i,  2;  1899,  5,  6. 
Heller,  J.  F.,  1837,  i. 
v.  Helmolt,  Hans,  1893,  2. 
Henry,  Louis,  1895,  8. 
Hermes,  1866,  2. 
Heusler,  Fr.,  1897,  5. 
Heyl,  Paul,  1894,  2. 
Hibbert,  W.,  1897,  6. 
Hober,  R.,  1898,  9. 
Hoist,  N.  OM  1873,  10. 
Hofmeister,  F.,  1859,  i. 
Howe,  James  L.,  1905,  i. 
Humpidge,  T.  S.,  1880,  3  ;  1883,  5, 

7  ;  1885,  i  ;   1886,  i. 
Itzig,  H.,  1899,  13. 
Jahn,  Hans,  1891,  5. 
John,  J.  F.,  1811,  2. 
Joule,  J.  P.,  1848,  i. 
Joy,  Chas.,  1863,  i. 
Karnojitsky,  A.,  1892,  5. 
Kahlbaum,  G.  W.    A.  and  Sturm, 

E.,  1905,  6. 
Klatzo,  G.,  1869,  r. 
Kiesow,  F.,  1898,  9. 
Kliiss,  K.,  1888,  2. 
v.  Kobell,  Fr.,  1832,  i. 
Kriiss,  Gerhard,  1890,  4,  5,  6,  7. 
Kiihne,  K.  A.,  1907,  4. 


Kurowski,  E.,  1907,  12,  13. 

Lacombe,  H.,  1901,  2  ;    1902,  3. 

Larsson,  Aksel,  1896,  10. 

Lavroff,  V.,  1884,  2,  3. 

Lea,  M.  Carey,  1858,  2. 

Lebeau,  P.,  1895,  2,  5;  1896,6;  1897, 

8;  1898,2,3,4,5,6,711899,  ii. 
Levi-Malvano,  Mario,  1905,  7. 
Lewy,  B.,  1857,  i. 
Ley,  H.,  1899,  10. 
Liebermann,  L.,  1896,  3  ;    1898,  15, 

16  ;    1899,  7. 
Link,  H.  F.,  1799,  3. 
Lockyer,  V.  N.,  1878,  10. 
McMahon,  C.  A.,  1892,  4. 
Mallard,  E.,  1887,  4. 
de  Marignac,  C.,  1873,  T- 
Mayrhofer,  Jos.,  1883,  3, 
Mendele"ef,  D.,  1879,  2  ;  1889,  3. 
Meyer,  Lothar,   1878,  5  ;    1880,  u  ; 

1887,  i. 

Meyer,  Stefan,  1899,  2,  3. 
Moissan,  Henri,  1898,  18. 
Moraht,  H.,  1890,  i,  4,  5,  7- 
Mosnier,  A.,  1897,  7. 
Miiller,  H.,   1853,  2. 
Myers,  Ralph  E.,  1904,  7. 
Neisch,  A.  C.,  1904,  6. 
Neumann,  G.,  1888,  i. 
Nicolardot,  P.,  1907,  8. 
Nielsen,  R.  A.,  1900,  2. 
Nilson,  L.  F.,   1875,  2,  3;    1876,  i, 

2  ;    1878,  2,  3,  4,  7,  8 ;    1880,  6, 

8,  9,  10,  12  ;  1884,  7,  8 ;  1885,  3. 
Noyes,  A.  A.,  1908,  2. 
Olmstead,  Charles  L.,  1906,  u. 
Ordway,  J.  M.,  1858,  i;  1859,  2. 
Ortloff,  W.,  1896,  12. 
Ouvrard,  L.,  1890,  n. 
Parkman,  Theodore,  1862,  i. 
Parsons,  Charles  Lathrop,  1904,  5; 

1904,  10,  n;  1905,  2,  4,  5;  1906, 

i,  13;  1907,  3,  10,  u. 
Pecile,  1877,  2. 
Penfield,  S.  L.,  1884,  i;  1886,  4. 


INDEX   OF   AUTHORS 


Perrey,  A.,  1888,  4,  5;    1890,  9,    10; 

1893,  I- 

Peroz,  J.,  1847,  i. 
Petersen,  Emil,  1890,  8. 
Petersen,  1899,  i. 
Pettersson,  Otto,  1878,    2,    3,  4,  8; 

1880,    6,    7,  8,  9.  10;  1884,  7,  8; 

1885,  3. 

Philipp,  J.,  1883,  2. 
Playfair,  L.,  1848,  i. 
Pollok,  James  Holms,  1904,  1,9,  12. 
Prudhomme,  M.,  1895,  7. 
Pozzi-Escot,  M.  E.,  1899,  4. 
Raikow,  P.,  1907,  14. 
Rammelsberg,  C.,  1891,  4. 
Rauter,  G.,  1892,  2. 
Reinsch,  H.,  1881,  2. 
Renz,  Carl,  1903,  3,  4. 
Retgers,  J.  \VM  1896,  4. 
Reynolds,  J.  E.,  1876,   3;    1880,    4; 

1883,  8,  10. 
Riess,  P.,  1845,  i. 
Rinne,  F.,  1895,  12. 
Rissom,  J.,  1898,  12. 
Rivot,  L.  E.,  1850,  i. 
Robinson,  W.  O.,  1906,  i;  1907,  10; 

1908,3. 

Roman,  R.  J.,  1898,  17. 
Roozebooni,  H.  W.  B.,  1891,  i. 
Rose,  G.,  1864,   i. 
Rose,  H.,  1827,  i;  1828,  i;  1842,    i; 

1843,  i;  1848,  2,3;  1855,  2,3. 
Rosenheim,  A.,  1897,  4;  1899,  13- 
Rossler,  C.,  1878,  9. 
Rowland,  H.  A.,  1895,  4. 
Rubenbauer,  J.,  1902,  5. 
Rydberg,  J.  R.,  1890,  13. 
Sarazin,  C.,  1892,  i. 
Schaffgotsch,  F.,  1840,  2. 
Schaub,  X.,  1801,  2. 
Scheerer,  T.,  1840,  3;  1842,  3. 
Scheffer,  G.,  1859,  3- 
Schlegelmilch,  F.,  1902,  4 
Schleier,  M.,  1892,  6. 
Sestini,  F.,  1888,  3;  1890,  2;  1891,  6. 
Seubert,  K.,  1893,  4. 
Smith,  Edgar  F.,  1878,   i;  1894,   2; 

1895,  9- 


Spear,  A.  B.,  1908,  2. 
Stein,  Gerh.,  1907,  9. 
Steinmetz,  Hermann,  1907,  5. 
Stolba,  Fr.,  1889,  i. 
Strohecker,  R.,  1886,  3. 
Stromeyer,  F. ,  1812,  i. 
Sturm,  E.,  1905,  6. 
Talnast,  R.  R.,  1895,  4. 
Tammann,  G.,  1885,  2. 
Tanatar,  S.  M.,   1904,  3;  1906,    10; 

1907,  12,  13. 
Thale"n,  Rob.,  1869,  2. 
Thenard,  L.  J.,  1811,  i. 
Thomsen,  J.,  1870,  i;  1871,  i;  1873, 

3;  1874,  2,  4. 
Toczynski,  F.,  1871,  2. 
Topsoe,  H.,  1872,  2;  1873,  5,  9- 
Traube,  H.,  1894,  i,  3. 
Trommsdorff,  J.  B.,  1833,  i. 
Ulpiani,  C.,  1899,  14. 
Urbain,  G.,  1901,  2. 
Van    Bemmelen,    J.    M.,    1882,    2; 

1898,  19. 
Van  Oordt,  G.,  1903,  5;  1904,  2,  4; 

1906,  5,  7- 
Vauquelin,  L.  N.,  1798,  i,  2,  3,  4,  5; 

1799,  i,  2. 

Vincent,  Camille,  1880,  2. 
Vogel,  Fritz,  1903,  2. 
Wagner,  J.,  1890,  12. 
Walden,  P.,  1894,  7. 
Wall  worth,  K.  A.,  1883,  i. 
Warren,  H.  N.,  1895,  10. 
Way,  A.  F.,  1899,  5,  6. 
Weeren,  J.,  1854,  i. 
Weinland,  R.  F.,  1902,  4. 
Welkow,  A.,  1873,  3,  4,  5,  6. 
Wells,  H.  L.,  1889,  2;  1901,  3. 
Wetherel,  E.  W.,  1904,  8. 
Williams,  C.   G.,   1873,   2;  1877,    i; 

1880,  i. 

Winkler,  C.,  1890,  3;  1891,  3. 
Woge,  P.,  1897,  3,  4- 
Wohler,  F.,  1828,  2;  1864    i 
Wulff,  G.,  1889,  4. 
Wyrouboff,    G.,    1894,   5;    ^    I; 

1896,  i;  1902,  i,  2. 
Zimmermann,  A.,  1887,  5- 


INDEX. 


•  A 

Acetate,  basic,  prep,  and  prop.,  62,  1798,  5;  1858,  i;  1901,  2;  1902,  3;  1903,  5  ; 

1904,  3,  4,  5  ;  1906,  i. 

basic,  double  with  basic  butyrate,  64,  1907,  12. 
basic,  double  with  basic  propionate,  64,  1907,  12. 
normal,  prep,  and  prop.,  40,  1907,  5. 

Acetylacetonate,  prep.,  prop,  and  analysis,  40,  1894,  6;  1904,  5. 
Acid  Salts,  discussion,  45. 
Absorption  spectra,  13,  1900,  3. 
Alexandrite,  artificial,  1887,  4. 
Alloys,  prep.,  15,  1896,  3  ;  1898,  17,  18;  1899,  7,  u. 

with  Cu.,  15,  1897,  8 ;  1898,  2,  4. 
Aluminate,  39,  1851,  3. 
Aluminum  plat,  chloride,  1874,  5. 
Antitnonate,  38,  1887,  2. 

Apparatus  for  electrolytic  prep.,  12,  1894,  4. 
Arc  spectra,  13,  1883,  5  ;  1895,  4. 
Arsenate,  ortho,  38,  1875,  4. 

acid,  45,  1875,  4. 
Arsenide,  prep.,  15,  1828,  2. 
Atomic  volume,  oxide,  23,  1855,  3. 

Atomic  weight,  14,  1815,  i  ;  1826,  i  ;  1842,  2  ;  1854,  i ;  1855,  i  ;  1869,  i  ;  1876, 
3  ;  1878,  5,  6,  8;  1880,  6,  7,  8,  11,  12  ;  1881,  i  ;  1882,  i  ;  1883,  4,  7,  8,  9, 
10 ;  1884,  5  ;  1885,  i ;  1886,  i  ;  1890,  i,  6,  7  ;  1904,  3,  5,  8  ;  1905,  5. 


Bacteria,  action  on  nitrates. 

Basic  Acetate,  62,  1903,  5  ;  1904,  4,  5  ;  1906,  i  ;  1907,  5. 

prep.,  prop,  and  analysis,  1901,  2  ;  1902,  3  ;  1904,  5. 

Butyrate,  prep,  and  prop.,  64,  1902,  3  ;  1907,   12. 

Formate,  prep,  and  prop.,  64,  1902,  3;  1907,  12. 

Isobutyrate,  prep,  and  prop.,  64,  1902,  3. 

Isovalerate,  prep,  and  prop.,  64,  1902,  3. 

Oxalates,  66,  1906,  i. 

Propionate,  prep,  and  prop.,  64,  1902,  3  ;  1907,  12. 

Sulphates,  See  Sulphate,  basic. 
Basic  Salts,  discussion,  61,  1906,  i  ;  1907,  4. 

list  of,  1906,  i  ;  1907,  4. 
Basic  Solid  Phases,  indefinite,  65,  69. 


INDEX  173 

Benzoate,  basic,  71,  1907,  12. 

Beryl,  artificial  production,  1873,  3  ;  1893,  I  ;  1893,  4. 

preparation  of  beryllium  compounds  from,  4. 
Beryl,  decomp.  of,  1801,  2 ;  1855,  i ;  1859,  3  ;  1863,  i  ;  1884,  i  ;  1889,  i ;  i893> 

3  ;  1895,  3,  5,  6  ;  1898,  5  ;  1902,   2. 

Beryllium  ethyl,  39,  prep,  and  prop.,  1860,  i  ;  1861,  i ;  1873,  I. 
methyl,  39,  1884,  2,  3. 
metallic,  preparation  12.     See  metal, 
chloride  quinoline,  20,  1903,  3. 
propyl,  39,  prep,  and  prop.,  1873,  i. 
Beryllonates,  27. 

Beryllonite,  method  of  analysis,  1889,  2. 
Borate,  basic,  70,  1878,  i  ;  1890,  i,  4,  5. 
Borocarbide,  26,  1898,  7. 
Bromate,  29. 
Bromide,  metal  from,  11,  1895,  10. 

prep,  and  prop.,  21,  1828,  2  ;  1831,  i  ;  1879,  r  »  1880,  i  ;  1884,  9,  10  ; 

1899,  n. 

vapor  density,  1886,  i. 
Butyrate,  basic,  prep,  and  prop.,  64,  1902,  3. 

basic,  double  with  acetate,  64,  1907,  12. 

C 

Camphor  Sulphonate,  44,  1894,  7. 
Carbide,  discussion  formula,  1895,  8. 

prep,  and  prop.,  26,  1895,  2;  1897,  5  ;  1899,  n. 
Carbonate,  magnetic  properties,  1899,  3- 

prep,  and  prop.,  38,  67,  1798,  5  ;  1840,  2  ;  1854,  i;  1855,  i;  1862,  i; 
1869,  i  ;  1890,  2  ;  1893,  4;  1904,  i;  1904,  5; 
1906,  4  ;  1907,  14 ;  1908,  3. 
action  of  NH4C1  upon,  1848,  3. 

Carbonates,  double  with  alkalies,  53,  1855,  l  \  J869,  i  ;  1886,  i. 
Chlorate,  29,  molecular  solution  volume,  1894,  3. 
Chloride,  19. 

hydrolysis  of  17,  21,  1899,  Io  >  I9°°>  T- 
taste  due  to  cation,  21,  1898,  9. 
basic,  70,  1873,  7,  8  ;  1875,  4. 
with  ether,  20,  1875,  4. 
double  with  Tl,  48,  1888,  i. 

anhydrous,  prep,  and  prop.,  19,  1827,  i  ;  1828,  2  ;  1842,  2  ;  1855,  i  ; 

1869^  i  ;  1880,  6,  7,  8;  1885,  3;  i887; 
I  ;  1897,  i;  1898,  5;  1899,  n;  1904, 
i;  1904,  5;  1904,  12. 


174  INDEX 

Chloride,  double  with  Hg,  Sn,  Au,  47,  48,  1873.  7>  8. 

hydrous,  20,  1842,  2  ;  1873,  7  ;  1873,  8. 

double  of  Hg  and  Be,  47,  1828,  4. 

double  with  Fe,  48,  1888,  i. 
Cr,  48,  1888,  i. 
I,  48,  1902,  4. 

reduction  by  electricity,  1831,  2. 

metal  from,  11,  1895,  u. 

fractional  sublimation,  20,  1905,  3. 

melting  point,   20,   1879,    i;   1880,  i;    1884,9,  IOI    I9°4»    J>  9- 

vapor  density,  20,  1884,  7,  8;  1885,  3  ;  1886,  i. 

basic,  preparation,  1798,  5;  1801,  i. 

heat  of  formation,  20,  1904,  9. 

heat  of  solution,  20,  1904,  9. 

action  upon  colloidal  As2S3,  1903,  i. 

magnetic  prop.,  1899,  3. 

molecular  wt.  in  pyridine,  1897,  4. 
Chloropropionate,  basic,  71,  1908,  i. 
Citrate,  basic  preparation,  71,  1798,  5. 
Citraconate,  44,  1907,   12. 
Chromate,  basic,  70,  1811,  2  ;  1873,  7,  8  ;  1907,  4. 

normal,  35,  1907,  4. 
Chromite,  35,  1887,  4. 
Columbate,  38,  1896,  10. 
Complexity  of  beryllium,  1904,  12;  1905,  4. 
Crystals  in  blowpipe  bead,  1898,  13. 
Crysoberyl,  prep.,  1890,  9. 
Crotonate,  basic,  70,  1907,  12. 
Cyanacetate,  basic,  70,  1908,  i. 
Cyanides,  26,  1871,  2;  1873,  1  \  l89^,  6;  1899,   n. 
Cymophane,  artificial  production,  1851,  3. 


Detection,  6,  1799,  i. 

Determination  in  beryl,  6-9,  1798,  i,  3,  4;  1823,  2. 

Determination,  in  monazite,  1896,  8 ;  1898,  10. 

Determination,  (See  also  Separation)  9,  1866,  3  ;  1880,  2  ;    1881,  3  ;    1897,    4  ; 

J9°3,  4 ;  1906,  2,  9. 
Dichloracetate,  basic,  70,  1908,  i. 
Dimethylamin,  action  on  Be  salts,  6,  1880,  2. 
Diplato-nitrite,  52,  1876,  2. 
Discovery,  1,  1798,  i,  3.     See  also  1801,  i,  2. 
Dithionate,  34,  69,  1888,  2. 
Double  Salts,  discussion,  47. 


INDEX  175 


Emerald,  artificial,  1877,  i  ;  1888,  4. 

coloring  matter  of,  1864,  i  ;  1873,  3. 

artificial  production,  1873,  3. 

color  of,  1857,  i. 
Ethylglycolate,  basic,  71,  1908,  i. 

F 

Ferrocyanide,  39,  70. 

Ferricyanide,  39,  1871,  2  ;  1873,  7. 

Fluoride,  prep,  and  prop.,  18,  1823,  i  ;  1869,  i  ;  1898,  8 ;  1901,  3  ;  1904,  i. 

prep,  of  metal  from,  12,  1898,  3,' 4  ;  1899,  u. 

double  with  K,  Na  or  NH4,  49,  50,  1823,  i;  1842,  2;  1855,  i;  1864,  3; 

1873,  2;  1893,  2;  1898,  3, 4;  1899,  ii. 
Fluosilicate,  prep.,  39,  1823,  i. 

Formate,  basic,  prep,  and  prop.,  40,  64,  1902,  3;  1907,  12. 
Fumarate,  basic,  44,  1907,  12. 


Glycolate,  basic,  71,  1908,  i. 

H 

Halides,  double,  18,  1901,  3. 
History,  2. 
Hydride,  1891,  3. 
Hydroxide,  27. 

basicity  of,  28,  1899,  10. 

Hydroxides,  prep,  and  prop.,  27-28,  1840,  i,    2;    1854,    i;    1855,    Jl     ^T1.   2J 

1873,  7,  8;  1874,  i;  1880,  2;  1882,  2;  1891,  6; 
1895,  7;  1898,  19;  1902,  5;  1903,  4;  1904,  2. 
Hydroxide,  magnetic,  prop.,  28,  1899,  3. 

heat  of  neutralization,  28,  1871,  i;  1874,  2;  1890,  8. 

solubility  in  beryllium  salts,  27,   1904,  10;    1906,  i;    1907,  10,  u. 
Hydrolysis  of  salts,  17,  1899,  10;  1900,  i;  1904,  10. 
Hypophosphate,  37,  1891,  4. 
Hypophosphite,  prep.,  37,  1828,  i. 


Incandescent  oxide,  1900,  2. 

Iodide,  prep,  and  prop.,  22,  1828,  2;  1855,  i;  1898,  6;  1899,  11. 

double  with  Pb,  50,  1897,  7. 

double  with  Bi,  50,  1874,  6. 
lodate,  29. 

Isomorphism  of,  1896,  4. 
Isobutyrate,  basic,  prep,  and  prop.,  64,  1902,  3. 


176  INDEX 

Isocrotonate,  basic,  70,  1907,  12. 

Isovalerate,  basic,  prep,  and  prop.,  64,  1902,  3. 

K 

"Krokonate,"  44,  1837,  i. 

I* 

Lactate,  basic,  71,  1908,  i. 
Laevulinate,  basic,  70,  1907,  12. 

M 

Magnetic  properties,  1899,  2. 
Maleate,  basic,  44,  1907,  12. 
Mallates,  59,  1899,  13. 
Mercury  cathode,  sep.  by,  8,  1904,  7. 
Mercuric  oxide,  action  on,  1894,  2. 
Metal,  11,  1898,  i;  1899,  n. 

by  electrolysis,  11,  1895,  10,  n;  1898,  3;  1899,  11. 
crystal  from,  12,  1884,  4;  1895,  12. 

prep,  and  prop.,  11,  14,  1809,  i;  1812,  i;  1828,  2,  3;  1855,  i;  1867, 
i;  1876,3;  1878,  3,  4;  1880,  6,  7;  1883,  7; 
1886,  i;  1890,  i,  3,  4,  5;  1892,  3;  1896, 
2;  1898,  i,  4,  14,  15,  16,  18;  1899,  ii ;  1904,  i,  9; 
1907,  2. 

Sp.  Gr.,  12,  1855,  i;  1878,  3,  4;  1886,  i;  1898,  3;  1899,  11. 
Microscopical  analysis,  1881,  2;  1883,  6;  1891,  2;  1892,  4;  1899,  4. 
Minerals,  Chief,  3. 
Molybdates,  basic,  70,  1873,  7,  8. 
double,  52. 
normal,  35,  1897,  4. 
acid,  46,  1873,  7. 

Monobromacetate,  basic,  71,  1908,  i. 
brompropionate,  71,  1908,  i. 
chloracetate,  71,  1908,  i. 

N 

Name,  origin  and  discussion  of,  1,  1798,  i,  3,  4;  1799,  3;  1904,  11;  1905,  i,  2; 

1907,  8. 
Nitrate,  hydrolysis  of,  17,  1900,  i. 

basic,  preparation  and  prop.,  70,  1798,  5;   1801,  i;  1858,  i;  1859,  2<  3; 

1904,  5- 

tetrahydrate,  normal,  36,  1906,  13. 
Nitrite,  37,  1903,  2. 
Nitroprusside,  39,  1871,  2. 

Nitroso-/3-Naphthol,  action  on,  7,  1892,  6;  1895,  9;  1896,  7. 
Normal  compound,  discussion,  17. 


INDEX  177 

O 

Occurrence,  3. 

Optical  rotation  of  mallates,  58,  1899,  13. 

camphor  sulphonate,  44,  1894,  7. 
tartrates,  57,  1899,  13. 
Optical  properties,  sulphate,  1889,  4. 
Oxalate,  acid,  46,  1902,  i;  1906,  i. 
Oxalates,  basic,  66,  1873,  7,  8;  1906,  i. 

Oxalate,  double  with  K,  Na  or  NH4,  54,  1855,  i;  1883,  2;  1897,  4. 
double  with  K,  Rb,  Na,  Li,  54,  56,  1902,  i. 
normal,  41,  1902,  i;  1906,  i. 

Oxide,  23,  1798,  2;  1851,  2;  1855,  i;  1884,  6;  1896,  6. 
action  of  NH4C1  on,  25,  1848,  3;  1855,  2. 
action  of  CC14  upon,  24,  1887,  i. 
action  of  bromine  on,  24,  1834,  i. 
action  of  Cl  and  S2C12  upon  24,  1907,  7. 
atomic  volume,  1855,  3. 
composition,  1842,  i. 

crystals,  23,  1851,  i;  1855,  i;  1886,  2;  1887,4;  1890,  9,  14;  1895,  12. 
extraction  of  from  beryl,  4,  1893,  3;    1895,    5,   6;     1899,    i;    1902,    2; 

1904,  i,  9. 

magnetic  prop.,  24,  1899,  3. 
presence  in  diluvian  clays,  1886,  3. 
reduction  by  Mg,  24,  1890,  3;  1899,  n. 

Al,  24,  1898,  14,  20;  1899,   II. 

Sp.  Gr.,  23,  1802,  i;  1848,  2;  1851,  i;  1880,  9,  10;  1886,  2;  1890,  7. 
Sp.  heat,  24,  1880,  9,  10;  1906,  10. 

P 

Palladio  chloride,  49,  1874,  3,  6. 
Patent  for  prep,  of  Be,  1892,  3. 
Peculiarities  of,  1907,  3. 
Perchlorate,  1873,  7,  8. 
Periodate,  1873,  7,  8. 
Periodic  position,  15,  1879,  2;  1889,  3. 
Phenacite,  artificial,  1887,  4;  1888,  4;  1890,  14;  1893,  I- 
Phenylglycolate,  basic,  71,  1908,  i. 
Phosphates,  with  Na,  52,  1883,  i;  1890,  u. 
with  K,  52,  1886,  2;  1890,  ii. 
with  NH4,  52,  1878,  9;  1899,  8,  9. 
Phosphate,  acid,  45,  1859,  3;  J875,  4- 

ortho,  37,  1873,  7,  8;  1875,  4;  1890,  2. 

hypo,  37,  1891,  4. 

triple,  Na  and  NH4,  53,  1859,  3. 
Phosphite,  prep.,  37,  1827,  i. 

hypo,  37,  1828,  i. 


*7  INDEX 

Phosphide,  prep.,  25,  1828,  2;  1899,  u. 
Picrate,  43,  1858,  2;  1907,  6. 
Plant  food,  beryllium  as,  1891,  6. 

Platino-chloride,  48,  1870,  i;  1873,  2,  5;  1874,  4;  1876,  2. 
cyanide,  50,  1871,  2;  1873,  10. 

double  with  Mg,  50,  1871,  2. 
Plato-iodo-nitrite,  52,  1878,  7. 
Plato-nitrite,  52,  1876,  2. 
Potassium  berylonate,  27,  1890,  i,  4,  5. 
Presence  in  plants,  1888,  3. 
Propionate,  40. 

basic,  prep,  and  prop.,  64,  1902,  3. 

double  with  acetate,  64,  1907,  12. 
normal,  40,  1907,  12. 
Pyrophosphate,  37,  1859,  3;  1873,  7- 
double,  1847,  i. 

Q 
Quinoline  beryllium  chloride,  21,  1903,  3. 

Racemates,  58. 

Refraction,  atomic,  1896,  10. 

specific,  1896,  10. 

molecular,  of  sulphate,  31,  1897,  6. 
Rhodizonate,  44,  1837,  i. 

Salicylate,  basic,  71,  1908,  i. 
Seed  production,  beryllium  in,  1891,  6. 
elenate,  crystals  with  sulphate,  1872,  u;  1891,  r. 
crystal  character,  34,  1872,  i;  1873,  6,  9. 
prep.,  34,  1873,  7,  8. 
Selenide,  prep,  and  prop.,  25,  1828,  2. 
Selenites,  basic,  70,  1873,  7,  8. 
Selenites,  34,  45,  1875,  2,  3. 
Separation,  6,  1840,  i,  2,  3. 

electrolytic,  8,  from  Al  and  Fe,  1881,  3. 

from  Al,  6,  1798,  i,   3;     1840,    i;     1843,    2;     1844,     i;     1855,    i; 
1859,  i,    35     1863,    i;     1864,    3;     1877,     i;     1878,    9; 
1880,    2;    1886,   4;     1887,    5;     1895,    9;     1897,    i,     2; 
J903,  4,  5;  J904,  i,  4;  I9°6.  i,  7,  8,  12. 
from  Ce  group,  1843,  2;  1864,  2. 
from  Cr,  6,  1904,  7. 

from  Fe,  6,  1840,   i;    1842,  3;    1850,  i;    1866,  i;    1892,  6;    1894,  2; 
1895,  9;    1896,  7;    1899,  5,  6;    1903,    5;    1904,  i,    4,  7; 
1906,  i,  7. 
from  Ga,  1882,  3. 
from  Yt,  1802,  i;  1843,  i,  2;  1864,  2. 


INDEX  179 

Silicate,  with  Al,  54. 

with  Ivi,  54,  1901,  4. 

double  with  K,  54,  1888,  5;  1892,  i;  1896,  5. 
Silicates,  double  with  Na,  54,  1890,  10. 

production  of,  38,  1890,  9,  14;  1893,  i;  1907,  9. 

Silicide,  27. 

Silicon  tetra  chloride,  effect  on,  1892,  2. 
Silico-tungstate,  39,  1894,  5;  1896,  T. 
Solution  volume  of  sulphate  and  chlorate,  31,  1894,  3. 
Specific  heat,  13,  1876,  3;   1878,  2,  3,  4;    1880,  6,  7,  8;  1883,  7;  1886,  i. 
Specific  rotation,  malates,  60,  1899,  13. 
sulphate,        1891,  5. 
tartrate,  58,  1838,  i;  1899,  13. 
Spectra,  13,  1869,  2;  1875,  i;  1878,  10,  n;  1881,  4;  1883,  5;   1887,  3;   1890,  13; 

1895,  4;  1898,  n;  1900,  3;  1901,  i;  1905,  3;  1906,  ii. 
Succinate,  normal,  43,  1873,  7,  8. 

basic,  70,  1873,  7,  8;  1907,  12. 

Sulphate,  anhydrous,  29,  1880,  9,  10;  1896,  6;  1899,  n;  1904,  10;  1905,  7. 
Sulphate,  basic,  65,  1798,  5;  1801,  i;  1815,  i;  1873,  7,  8;  1904,  10;  1907,  10,  u. 
Sulphate  dihydrate,  30,  1854,  i;  1880,  6,  9,  10;  1890,  7;  1904,  5,  10;  1905,  7. 
Sulphate   heptahydrate,  33,  1869,  i;  1873,  i;  1904,  10. 
Sulphate  hexahydrate,  32,  1873,  JI  I9°5.  75  1906,  5- 
Sulphate  monohydrate,  30. 
Sulphate   tetrahydrate,  30. 

crystals  with  selenate,  1872,  i;  1873,  6;  1891,  i. 

heat  of  solution,  32,  1873,  4>  I9°4>  9- 

hydrolysis  of ,  31,  1899,  10;  1900,  i;  1904,  10. 

magnetic  susceptibility,  31. 

mol.  refraction,  31,  1897,  6. 

mol.  solution  volume,  31,  1894,  3. 

mol.  volume  32,  1873,  6. 

mol.  wt.,  1880,  9,  10. 

prep,  and  prop.,  30-32,  1815,  i ;  1842,2;  1854,  i;  1855,  i;  1872,  i; 
1873,  7,  8,  9;  1880,  6,  9,  10;  1889,  4;  1890,  7; 
1899,  3;  1903,  i;  1904,  i,  5,  9,  10,  12;  1905,  7. 

solution  friction,  31,  1890,  12. 

solution  in,  32,  1907,  n. 

specific  gravity,  32,  1872,  i;  1873,  6;  1880,  9,  10;  1890,  7. 

specific  rotation,  31,  1891,  5. 

taste  due  to  cation,  31,  1898,  9. 

Sulphates,  double  with  K,  NaorNH4,  51,  1842,  2;  1855,  i;  1869,  i;  1873,  2>  7.  8- 
Sulphide,  double,  of  Be  and  W,  50,  1826,  2. 

preparation,  25,  1825,  i;  1828,  2;  1853,  i;  1855,  i;  1899,  u. 


l8o  INDEX 

Sulphite,  normal,  33,  1890,  i,  4,  5. 

basic,  69,    1873,  7,  8;  1890,  4;  1893,  4. 

double  with  K,     52,  1897,  4. 
NH4  52,  1897,  4. 

Sulphocyanate,  34,  1866,  2;  1871,  2;  1873,  7- 
Sulphonate,  44,  alpha  brom  camphor,  optical  rotation  of,  1894,  7. 

T 
Tartrate,  42,  1871,  2;  1873,  7J  l873>  8- 

basic  preparation,  71,  1798,  5. 

mono  and  di,  56,  57,  1899,  13. 

rotatory  power,  1838,  i;  1899,  13. 

double  with  K,  Na,  NH4,  1897,  4;  1899,   13. 
Tellurate,  35,  1833,  2. 

Telluride,  25,  prep,  and  prop.,  15,  1828,  2. 
Tellurite,  35,  1833,  2. 
Thiosulphate,  34,  1901,  5. 
Trichloracetate,  basic,  71,  1908,  i. 
Trinitride,  25,  1898,  12. 

V 

Valency  discussion,  15,  1826,  i;  1832,  i;  1842,  2;  1843,  3;  *%55>  i,  2,  3;  1875,  2; 

1876,  i;  1878,  3, 4,  5,  6;  1880,  3,  4,  6,  7,  8,  11,12;  1881,  i; 

1882,  i;  1883,  5;  1884,  7;  1894,  5,  6;  1895,  i,  7,  8;i897,  4; 

1902,  i;  1904,  3;  1906,  10;  1907,  i,  6. 
Valerate,  71,  1833,  i. 
Vanidate,  38,  1831,  3. 

Vapor  tension  of  solutions  of  Be  salts,  1885,  2. 
Use  in  incandescent  lamps,  1896,  9. 


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